I don't understand why the publishers of many of these classic games continue to let their games be sold as collector's items, rather than re-issuing the games themselves, and making more money off them. I'm not going to include multi-disc PS1 titles in this list, since I'm not sure the PS3/PSP emulator is even capable of running them.
Why don't these titles make an appearance? I'm sure I'm missing a zillion of them... these are just off the top of my head. I wish I'd see games like Suikoden, Suikoden II, Tales of Destiny, Xenogears, etc. but they're not from Square-Enix, so I'm not including them either.
RPGs are one of the few genres to have really "durable" appeal, so it seems as though they should dominate the VC/PSN market...
Secret of Mana
Final Fantasy IV, V, VI
Ps1 classics for PS3/PSP, via PSN:
Legend of Mana