Title track from Sin: Emergence - "What's The World Come To". Vocals by Sarah Ravenscroft. Composed by Zak Belica.

It's a very neat piece.

Samurai Western - opening song (It even has the singer from the animes in it!)

bump!

Drawn to Life - The End
Two Worlds - Play The Game

Sam & Max! I just recently started listening to Jared Emerson-Johnson's Sam & Max Season One Soundtrack, and there are some great vocal songs on there.

"Just You And Me (and Ted E. Bear)" - Clever song with three characters singing about how they are legitimate businessmen, not mobsters (ha).

Also, there are a few on disc 2, but I haven't really delved into that disc yet:

"Good for You (Good for Me)"
"Useful to Boot"
"World of Max"

EDIT: Whoops, one from disc 1 I forgot: "More Than Jerks"