We spent three weeks in France when my daughter was 8 months old, one week of it being in Avignon. I'd recommend 3-4 days in Avignon, a week was a bit too long, though if you have a car, you could easily do some nice day trips from there. We only did one mini-bus tour (Arles, Orange, brief stop in CNP), should have done a second, but everything was booked up when we tried.
RE: Having a car: the only warning I'll give you is that Avignon has the narrowest "streets" I've ever seen and I've been in a bunch of European cities. Dear lord, it was scary driving there and parking is an absolute premium inside the walls. For accommodation, we rented an apartment inside the walls and it was great. This was three years ago now, but if you'd like, PM me and I can see if I can find the rental details.
Have fun! We have travelled the world with our now 3 year old and have zero regrets.
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