Cynthia (Pokemon) - She's an agreeable woman whose hobby is the study of mythology in the Pokemon world. Even if nothing romantic were to arise from the encounter, just the conversation alone would be worth one of my five slots.
Lux (League of Legends) - She's an upbeat person that seems like she'd be a lot of fun to spend time with and get to know
Maria (Star Ocean) - I like her drive and how direct she can be, and I'd love to get to know her better.
Aerith - She's a little playful, a little daring, and always struck me as a fun person.
Judith (Tales of Vesperia) - Pretty much the same as Aerith, only moreso in every way.

For hanging out
Cynthia, for the same reasons as above.
Galuf, because I can't imagine a world where this isn't hilarious
Minsc, See above. Only moreso.

Sadly, another two aren't coming to mind. Perhaps later.