San Sebastian (really Donostia before being given a Spanish name) is a nice town, but needs to be visited in the high summer months (July/August) because it's rainy and chilly the rest of the year. The down side, as acraven points out, it may be harder to get to and burn too much of your valuable time. There are some very good seafood places in Donostia and bars that serve great "Gintonics" (one word, the other popular drinks are beer, wine and mojitos). Potential daytrips - with a car - are Pamplona, Saint Jean Pied de Port, Bilbao, Olite Castle or a wine museum in Vitoria Gasteiz. Wineries need advanced reservations one or two days ahead, they aren't open like American wineries (maybe some are open in July?).
Barcelona is a good city to visit. I think you can cover quite a bit (not everything) in three days/four nights. Even more in four full days. I'd spend one day exploring the Barri Gothic, another exploring Modernista architechture (including Parc Guell and Sagrada Familia), a third day in town (maybe Mt. Juic?) is not too much but can also be used for a day trip to either Montserrat or some combination of Costa Brava/Girona/Figueres. For Montserrat without a car, stop by any bus station and book a seat on one of their day trips. For Costa Brava a train is easy. There may be daytrips on buses to Girona/Figueres but I haven't done it. My favorite tapas bar is El Xampanyet, most of the others are chains (IMO over-rated).