Avignon is beautiful, the most attractive town of its size (ie, rather big) that I know. However hop off the TGV at Orange, it's significantly closer and pleasanter onward trip to Malaucene, or Bedoin, for Ventoux. From Avignon it's not too good by bike, owing to Carpentras being in the way. I have detailed laney GPX from Orange to Bedoin via Beaumes, should you want.