[3.P] Statting up League of Legends champions

[ImperatorK]

Katarina The Sinister Blade - she's probably the easiest, Bloodstorm Blade is just perfect for her. Blood Wind Ricochet for Bouncing Blades. One of the Shadow teleport maneuvers for Shunpo, preferably the move or swift action one, or maybe the standard action with Shadow Pounce. Blade Storm plus Thunderous Throw is the ult, Death Lotus.

Annie The Dark Child - Summoner with a few Extra Spell feats for fire spells like Fireball for Disintegrate, Buring Hands for Incinerate and Fire Shield for Molten Shield. Obviously the eidolon is Tibbers.

[ketaro]

Elise the Spider Queen - Vermin Druid variant with spider animal companion and Spider Shape ACF from Dungeonscape. If you need more spiders to have more spiders you could either dip Beastmaster or PF Summoner or get a spider swarm to keep it simple. You could also stack Entomanothropy into the mess for some vermin (Spider) lycanthropy.

I only know this because I accidentally made Elise in an E6 Gestalt Underdark campaign. I wanted all the spiders and did Drow Vermin Druid (Spider Shape variant) // Summoner and eventually dip Beast Heart Adept for an Ankheg refluffed as something more spiderlike so I'll have 3 strong pet spiders and Wild Shape into a big Spider whenever; and then my DM pointed out what I had done. Boy did I hate myself, but I'm still playing it and loving it.

[Chrononaut]

Garen is pretty obviously a nonspellcasting mountless Paladin with whirlwind attack. DEMACIAN JUSTICE is Smite Evil.

Jarvan IV... actually IIRC I'd say he's a bard using perform(oratory) in 3.5, though in PF he'd be cavalier with that banner of his.

[Gazzien]

Lucian is, of course, a [PF] Gunslinger (Pistolero), dual-wielding pistols and using Flare Cartridges for a couple of his abilities. The Freedom domain power (when needed, Freedom of Movement) combined with the Quick Runner's Shirt gives you his dash.

[Azrael]

Katarina The Sinister Blade - she's probably the easiest, Bloodstorm Blade is just perfect for her. Blood Wind Ricochet for Bouncing Blades. One of the Shadow teleport maneuvers for Shunpo, preferably the move or swift action one, or maybe the standard action with Shadow Pounce. Blade Storm plus Thunderous Throw is the ult, Death Lotus.

Annie The Dark Child - Summoner with a few Extra Spell feats for fire spells like Fireball for Disintegrate, Buring Hands for Incinerate and Fire Shield for Molten Shield. Obviously the eidolon is Tibbers.

I was thinking Kat would be more of a master thrower tef shadow lord type deal. Draven is the obvious master thrower.       

If you're playing with pathfinder Annie seems to obviously be a kineticist from occult adventures. One of the main examples for the class is even a little pyro girl with a strange stuffed animal she carries around. It seems to me the class was inspired directly by Annie so it would only be logical to make her one. As for Tibbers, there is actually a template in the 5th bestiary that has to do with some kind of soul-bound puppet.

Of course you wrote all this before OA was released so at the time it was likely a better solution.