I stayed at Camera Caffe B&B Centro for 2 nights in June.
I have never stayed in a B&B where the staff were so friendly and helpful.
From chatting over breakfast, to giving travel advice and to calling when there was last minute availability.
The B&B itself is in a very convenient position, right next to the train station and a short walk fron the historic centre.
Ideal if you want to be in the hub of Arezzo but if you want something a bit quieter then there is the sister B&B just outside the centre by a lake-Camera Caffe Sul Lago.(See separate review.)