My favourite place in Italy besides Rome is not Venice, Florence or Tuscany but the relatively obscure wine producing region of Barolo in Piedmont. This seems to run counter to most of the comments here, but Piedmont is the only region that has successfully grown and produced wine from Nebbiolo. 

The scenery is also beautiful and the wine some of the most complex in the world, but most importantly here you can meet some of the most hospitable people who work in the wine trade.