In my experience, riot does not agree with it, but you don't get in trouble directly for doing so.
If you go online you can find programs that will edit your character models or splash arts. the thing is that its only changing them for you, so everyone else will see the normal art/models.
As far as i know riot doesn't reeaally care about this but if you do end up doing this i would suggest not doing ranked until you reset the changed files because it can make you crash and reconnect sometimes. and patching is a hassle.
But if you can deal with that then feel free. you can look up skin tutorials on youtube fairly easily.