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Last of the Bunch
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League of Legends is known for having over 100 playable characters. Despite being the 100th Champion, Draven was not given any special announcement.

Jayce was the 100th Champion

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Thresh and Senna both have Soul-collecting mechanics, and interestingly, there are 2 Champions that drop 2 Souls upon death: Nunu and Sejuani.

Sejuani doesn't drop 2 Souls - only the boar drops a Soul, and Sejuani doesn't have a Soul, because she's a "Ginger"

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Slightly Magical Boots is an Item only available from the Magical Footwear Rune, and has the same stats as basic Boots, but instead of selling for 210g, it only sells for 90g

Slightly Magical Boots has 10 more movement speed (and carries over that 10 movement speed, when you upgrade them)

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Pay Cut is a Consumable Item that is only receivable from an ally Pyke, which grants 100 − 300 (based on target's kill bounty), increased by 100 for First Blood. Can be used while dead.

Your Cut is the actual name.

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Malzahar is one of the few Champions to have a "Pet," the others being: Annie, Heimerdinger, Ivern, Shaco, and Yorick

Elise also has a Pet(s) - her spiderlings 

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Despite Trinity Force being centered around 3s, it grants 5 different stats: AD, Ability Haste, Health, Mana, and Attack Speed

Only grants 4 stats (no longer grants Mana)

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There are several Champions whose dance is a reference to a TV show; examples of this include Amumu's dance, a reference to the goth kids in Family Guy, and Volibear's dance, a reference to Sam B. from America's Got Talent

The goth kids were from South Park

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Poros are little creatures in League of Legends with quite a few quirky gimmicks, including: growing facial hair when Graves feeds them a poro-snax, growing in size when fed (before their Porosplosion), and wearing party hats during League's 10-year anniversary.

Braum is the one who allows Poros to grow facial hair when fed

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Black Spear is a Starter Item for Kalista, and upon use the item disappears, but it can be repurchased at the store until 1:30 for no cost, enabling Kalista to use it on a different allied champion.

Can only be repurchased until 3:00mins 

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While most Champions rely on Mana, there are a few Champions who use their own Health as a resource, those Champions being: Aatrox, Dr. Mundo, Vladimir, and Zac.

Mordekaiser also uses his own Health as a resource

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Akali is the first Champion to have an emote that will orient itself the same (i.e. facing towards the camera), no matter what direction Akali was facing.

Yasuo was the first Champion (Akali was the second)

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It could be said that Riot gives more skins to the most popular Champions, and of those popular Champions, Ahri was the first to receive 12 skins (including Classic)

Annie was the first

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Yasuo, despite being inspired by a Japanese samurai, doesn't actually speak Japanese - he speaks an ancient Ionian language/dialect, such as when he shouts, "Sorye!" when using the 3rd cast of his (Q) Steel Tempest.

Yasuo shouts "Sorye!" when casting his (R) Last Breath.

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Winter's Approach is a Legendary Item, built from Tear of the Goddess, that grants the Unique Passive: Everlasting: Immobilizing, or slowing if you are melee, an enemy champion grants a shield for 3 seconds (8 second cooldown). The shield's strength is increased if there is more than one enemy champion within 1200 units. 

Fimbulwinter (the upgraded version of Winter's Approach) is the one with that Passive

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Yone & Yasuo are probably League of Legends' most popular pair of siblings, but League actually has 8 in total, the other 7 being: Jinx & Vi, Cassiopeia & Katarina, Garen & Lux, Kayle & Morgana, Nasus & Renekton, Anivia & Volibear, and Darius & Draven.

Anivia & Volibear are siblings, but they are not a "pair" of siblings - they have a third sibling, whom is Ornn.

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%Max Health True Damage is an extremely powerful form of damage, which is why it's limited to 1 Champion only: Vayne (and she's squishy)

Fiora also has %Max Health True Damage

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Aphelios is quite the unique Champion. He's the only Champion with a unique HUD, his two weapons allow for 9 different possible combinations, and he's the first Champion in the game with less than 4 abilities.

Aphelios has a total of 10 different combinations
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When Nocturne casts his W (Looming Darkness), he gains a Spell Shield for 1.5 seconds, and upon successfully blocking a hostile effect, Looming Darkness' bonus attack speed is doubled for 5 seconds.

Shroud of Darkness is Nocturne's W-name

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Runaan's Hurricane is a ranged Champion exclusive Item that grants the Unique Passive - Wind's Fury: Basic attacks on-attack fire 3 additional bolts at up to 2 enemies in front of you, each dealing physical damage. Bolts apply on-hit effects at 100% effectiveness and are affected by critical strike modifiers. 

Only fires (up to) 2 additional bolts

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Crowd Control is a powerful tool that can stop enemies in their tracks, but interestingly, there are a few Champions in League of Legends that can CC *themselves*, those Champions being: Xerath, Blitzcrank, Caitlyn, Lissandra, Malzahar, Rumble, Sion, Varus, Vi, and Ziggs.

Malzahar's (R) Nether Grasp does *technically* not CC himself

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In Summoner's Rift, Rabadon's Deathcap was once recommended as a situational item for Ashe, this was most likely a reference to the old Basic Tutorial where Ashe is pre-selected as the player's champion and D-cap is the only purchasable item. 

The actual item was Thornmail (for both)

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There are a few Champions in the game where their character model doesn't actually represent their real hitbox. One such example is Aurelion Sol, where his upper-body is not part of his in-game hitbox, which is why it is semi-transparent 

Aurelion Sol's *lower* body is not part of his hitbox 

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When Caitlyn and Vi are on the same team, they are granted the cosmetic buff "Catch Me If You Can." This buff gives them extra gold when they score a Takedown together.

On the Case is the name of their buff, when playing together.

Catch Me If You Can is the buff they receive if there's a Jinx on the enemy team. 

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Azir is not only the first Champion to be unable to rank up a basic ability at Level 1, but he's also the first Champion  to have his first ability point restricted to a single one, Arise! (W), since it's required for the other two abilities (Conquering Sands (Q) and Shifting Sands (E)) to function. 

Azir is the second champion to be unable to rank up a basic ability at Level 1, the first being Zilean.

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League of Legends used to have a Difficulty Rating System 1-10, 1 being the easiest to play, and 10 being the hardest. Anivia was one of six Champions to be rated a 10, the other five being: Cassiopeia, Evelynn, Rumble, Vayne, and Yasuo. 

Vayne was not rated a 10 in difficulty