On 1 July 2006, the first day of the free agency period, Chára signed a five-year, $37.5 million contract with the Boston Bruins and was named the team's captain, a role left vacant since Joe Thornton's departure during the 2005–06 season to San Jose. Chára became only the third Slovak-born NHL player to become a team captain, after Peter Šťastný of the Quebec Nordiques and Stan Mikita (co-captain) of the Chicago Blackhawks. Chára was named to the 2007 NHL All-Star Game (his second appearance) in Dallas and scored two goals in a 12–9 Eastern Conference loss. Chára also won the hardest shot segment of the preceding Skills Competition, clocking a shot at 100.4 mph. While his season was a personal success for many of these reasons, the Bruins were in a rebuilding mode at the time, and the signing was questioned throughout the NHL, as Chára posted an uncharacteristic −21 plus-minus rating that season due to the Bruins' struggles. However, his 32 assists were a new career high.