The Hotkeys I use for League - CLG Link

Normal Casting : Q/R/T/F // Brother used this set up. Spread out and I stuck with it cause we only had 1 computer. DotA hotkeys don't use this setup. Hotkeys change depending on hero to hero in DotA.

Smart (Quick) Casting: Z/X/C/V // Don't like 2 button presses. This way I can alternate between normal/smartcasting anytime.

Smart Casting Summoner Spells : D/E

Leveling up Spells:

skill1: Ctrl Q

skill2: Ctrl R

skill3: Ctrl T

skill4: Ctrl F | G // G because my ultimate is on F. If I play Ahri and I'm hitting 6 on the next creep I can press G -> F in quick succession.

Normal Casting Items : Space/4/5/6/7

Smart Casting Items : 3 // dfg/gunblade/bork

Center on My Hero : 1

Center on X Hero : 6 // Varies on game to game basis. Usually my jungler or AD. In LCS I'll have it on Doublelift to see where he is in a teamfight

Center on Other Heroes: F1/F2/F3/F4

Explanations/Individual [Weird?] Hotkeys

W = changes depending on the game. Might be smartcast Q when I play Ezreal. It might be smart+selfcast E when I play Nidalee

2 = Smartcast+Selfcast Ultimate for when I play heroes like Zilean/Lulu/Lisssandra/Jayce/Elise who have some sort of ulti that usually needs to be selfcasted i can always resort to this

Space = usually where I place my wards for lee sin. I'll press Space -> X or 5 -> R to ward hop.

Back mouse button : Smartcast/Selfcast Spell #2 (For Lee sin Shield)

Forward mouse button : Open shop