In LeBlanc's case, her name is French, so having a general idea of how French words sound helps. It's pronounced [luh-blonk], and it translates to "the white". As a member of the Black Rose, this was no doubt intentionally ironic.
As for Vi, that's actually pretty sensible as far as mistakes go. When it comes to long 'i' sounds, you'd expect it to come with a spelling like "Vai" or "Vye", or something along those lines. Assuming that "Vi" is as far as her name goes and isn't just shorthand for a longer name like Victoria or something (and it's not), a long 'e' sound seems logical for something that short. Of course, once you start playing her, you pick it up pretty quickly after hearing "Vi stands for violence!" a few times. xD
Yasuo's Japanese, so you'd expect his name would follow Japanese pronunciation. In general, Japanese vowels are pronounced the same in all instances and occurences. Put simply, a is "ah" ("ball"), u is "oo" ("tube"), and o is "oh" ("mode"). With consonants, his name is pronounced [yah-soo-oh]. Just to have the other vowels covered, e is "eh" ("fed"), and i is "ee" ("ski).
Don't ask about
though. I have no idea.