Well gouramis are probably my favorite group of fish, so I'm biased here, but a dwarf gourami would make a great addition to your tank. A male without females might chase the neons around, but IME is unlikely to do any damage. Check closely in the dealer tank when you buy dwarves though, if ANY of them look sickly, aren't moving or have an open sore, dont buy a Gourami from that store.
A safer bet with your neons is a "Honey" gourami (Colisa Sorta, or Colisa Chuna) Honey gouramis are a bit smaller and gentler than the dwarfs, but they can be harder to find. These are less likely to be ill at the store, but a little less hardy than C. Lalia once established IME - still fairly easy to keep though.
Pearl Gourami (Trichogaster leeri) would be nice too, they get a bit larger than the dwarf variety, but they are really shy usually. Only thing is, if you get one that's not shy, it could wreak havoc on your neons... but any Gourami *might* pick on them I suppose.
Gouramis, like cichlids, display a wide range of personality (fishinality??) even between individuals of the same species, so YMMV from fish to fish, but generally they're great aquarium fish.
Oh ya, there are a few varieties of Dwarf Gouramis, and the gold and sometimes the red (is red with a blue dorsal fin) varieties are thought to be a hybrid of the Dwarf and Honey. These "Dwarves" are thought to be less prone to the common Dwarf illnesses. So if you do decide to go with Dwarfs, try the red one for the safest experiance. I have a red one, and he's safe with all but the smallest killifish fry (he was in there to eat hydra 3 years ago - which he was a champ at BTW, but I just left him in the 2nd stage growout tank, that's how safe he is) very gentle fish, but not shy.
There are also some Gouramis, usually smaller 1.5-2.5 inches which aren't commonly seen, but would be good with neons. A couple of good bets there would be the Sparkling Gourami (Trichopsis pumilus) and the Licorice Gourami. These are very small, and are a little harder to keep, but with some research you would probably be okay. Liveaquaria.com used to have some "oddball" Gouramis, you could check there.