Or not Toulouse?.....Sorry.

I'm looking for French people's advice on Toulouse. I really like the look of it, it intrigues me. And more generally, how does it rank amongst French cities that are not Paris? I'm up for other suggestions, just I know Paris and am looking to explore more cities and regions. Also, if you were heading to either the extreme south-west or extreme south-east coast, from here, ie Bayonne/Biarritz or Perpingan, French Catalonia area, where would you recommend?