No, you can be excused (this time ) because most of Neville's reputation outside of the "deep" fans has come in the last 15-20 years or so, and it's been through (mostly) cheesey material & productions. But the cat's got a deep history, and a deep legacy.
The compilation pictured above is a good enough sampling of the prime early stuff (Allan Toussaint's all over it, and that's usually a good thing, at least back then), but there's others. Nothing comprehensive yet that I know of, but it's mostly all good - mid-late 60s New Orleans R&B of the finest variety. If Lee Dorsey was Tousaint's Mustang, always ready toi hit the streets and rumble, then Neville was his pimped out Lincoln, plush on the surface but deadly when needed.
For something later, check out two of the Neville Brothers A&M sides Yellow Moon & Brother's Keeper. Neitehr are consistently great, but they are often enough.
Oh yeah, he had a solo album with that insipid hit cover version of "Everybody Plays The Fool", but it also had a killer version of John Hiatt's "It Feels like Rain" and an ethereal-out-the-ass reading of "Ave Maria". The "yodel" thing is in there, so be forewarned.
But dude, Aaron Neville has paid some dues and reeks of soul when he's not making records that just reek, period.