I'm the kind of guy who knows a champ for its skin
So what I did is I browsed through my LOL files to the champion images page, and sought out Jinx. I rather like the face on her Firecracker Skin, its fresh and really easy to find because of the red background (red catches the eye better, as proven by science) with her green highlight (bright freaking green, also kinda hard to miss).
Booted up Photoshop, and created a square and filled it in with black paint, then edited out the insides and added blur to mimic the border. Created a new layer, imported that over an HD Firecracker Jinx wallpaper I had gotten, and used my magic wand tool to copy the border and its insides, giving me a 120x120 selection. Clicked on the layer that has the wallpaper. Now that I have the selection from the previous layer (which prevents me from randomly collecting random tidbits of the actual splash while also giving me the ability to move the selection around without pulling apart the splash) I CTRL-C over a decent looking area of her head, and opened a new document using my clipboard as its foundation.
CTRL-V and her head is done. Go back to my border Photoshop document and copy that. Create a new layer on my Jinx's head, and paste. Saved it all up. Backed up my original Jinx files, and copied the new ones over. Now in champ select, I can easily find her.
NOTE: This doesn't change the in-game face, this is purely client side. The only NOTICEABLE effects are the splash page (the upper right hand square for the champion portrait) and champion select pool. Basically, when you view Jinx in the store or in the champions list in the client, her face will still be normal, but if you directly open up her page, her square portrait will be the one that was replaced. The square is also replaced for the champ pool and when you "hover over" her.
This shouldn't be against Riot's TOC, unsure about it, all I know its kinda-sorta like a custom skin (well, more like custom icons) and Riot hasn't outright said no to custom skins (they won't be held responsible if something goes wrong though. Essentially neither for nor against).
Also: unsure if this is a skin/champ concept thing or just misc things. Better safe than sorry, hence I'm posting in misc. discussion.