The Italian becomes the team's third domestic champion, with Josh Waters (double Australian) and Ryuichi Kiyonari (Asian Road Race) also on the roster for next season.
Baiocco, who has twice won the Italian Superbike championship, has had a taste of BSB before, first visiting Caldwell Park last year before deputising in a one-event debut at Silverstone for Moto Rapido Ducati.
"I am very happy to join Moto Rapido," Baiocco said. "We have been working on this together for a long time and I really want to thank Steve Moore for the opportunity.
"During 2012 I had already got to know the team and BSB; I like the team very much and I was excited to race in BSB. This will be a very important season for me after winning in Italy."
Team owner Steve Moore added: "He is quite a character and I am sure the BSB fans will love him. Matteo is twice Italian Superbike champion with Ducati and his strong links to the factory brings increased technical support from Ducati Corse.
"With the upgrade to the 1199R Panigale this year we are expecting to progress well. We are still a new team so the challenge has been huge, but this season is looking stronger than ever for us and we have more exciting news still to come."