Chara, 29, was a major off-season signing by the Bruins after he left Ottawa as a free agent. The only other Slovak-born players in league history to wear a C on their chests were Peter Stastny (Quebec Nordiques) and Stan Mikita (Chicago Blackhawks).
"Zdeno's leadership qualities have been apparent from the time he joined players for their informal skates prior to training camp," GM Peter Chiarelli said in making the announcement Tuesday. "He leads by example, both on and off of the ice, and he has earned the respect of everyone in our dressing room.
"He recognizes the leadership abilities of his two assistant captains as well as other players, and he also realizes that every player has strengths that they bring to our team and that bringing those strengths together is crucial to our success."
Boston had been without a captain since trading Joe Thornton last Nov. 30.
Joe Sakic begins the new season as the NHL's longest-serving captain. The 37-year-old centre inherited the distinction when Steve Yzerman retired after 20 years in the role with Detroit.
Sakic was named captain of the Nordiques in 1992, and he has continued to lead the team since it moved to Denver and became the Colorado Avalanche in 1995.
Mats Sundin, captain of the Toronto Maple Leafs since 1997, has the second-longest tenure.
Montreal's Saku Koivu and Ottawa's Daniel Alfredsson assumed the responsibility in 1999, Vancouver's Markus Naslund has had the distinction since 2000, Edmonton made Jason Smith captain in 2001 and Calgary gave the C to Jarome Iginla in 2003.
Others continuing on in the captain's role are Scott Niedermayer in Anaheim, Olli Jokinen in Florida, Shane Doan in Phoenix, Patrick Marleau in San Jose, Mattias Norstrom in Los Angeles, Scott Mellanby in Atlanta, Alexei Yashin of the Islanders, Dallas Drake in St. Louis, Adrian Aucoin in Chicago and Rod Brind'Amour of the Hurricanes.
"Rod is by far the best captain I've ever played with," says Carolina forward Eric Staal. "He's a guy that's going to say things at the right time.
"He let you do what you need to do to get prepared but he's not going to let anything slide. He's the hardest-working player I've ever seen and you need that, especially from your captain. he's just a great guy all-around and we're so lucky to have him as our leader."
Ten of the 30 teams will have new or no captains.
Centre Peter Forsberg takes over in Philadelphia from the retired Keith Primeau and says he hopes to emulate Sakic, with whom he won the Stanley Cup in 1996 and in 2001. Forsberg plays a rambunctious style of hockey, but he's not a screamer.
"Joe wasn't real vocal either," says Forsberg. "He led by example.
"He was always the last one off the ice. He doesn't need to scream and yell. He's just a great captain, a great leader."
Adam Foote, a key cog on defence on those championship Avalanche rosters, is captain of the Columbus Blue Jackets.
Brenden Morrow was named captain of the Dallas Stars, taking over from Mike Modano who wore the C since 2003. Modano didn't hide his disappointment but said it wouldn't effect his play.
Nicklas Lidstrom is expected to succeed Yzerman in Detroit, although the Red Wings are being coy.
"We're going to name a captain opening night," coach Mike Babcock said during training camp.
Nashville, replacing Greg Johnson who now is with Detroit, named Finnish defenceman Kimmo Timonen its new captain.
"Kimmo is a top player on this team and in the NHL," said coach Barry Trotz. "He is an original Predator, has been a big part of the growth of this franchise, and has been a strong leader for us for a long time."
Jaromir Jagr is expected to be named captain of the New York Rangers.
Tim Taylor is the new captain of the Tampa Bay Lightning and Chris Clark takes over in Washington.
New Jersey went without a captain last season and nobody has been tabbed for the C thus far.
The Minnesota Wild select a different captain each month.
Pittsburgh has decided it won't have a captain.
"The biggest reason why is out of respect for what Mario Lemieux did for this franchise," explained head coach Michel Therrien. "We'll keep doing what we did after Mario retired last year."
Teen sensation Sidney Crosby will ascend to the post, but not quite yet.
Taylor, a third-line centre, is an excellent example of a team opting for a player with a strong work ethic rather than star status to wear the C.
Taylor got to know some of the most respected captains in recent league history as a teammate of Yzerman in Detroit, Ray Bourque in Boston and Mark Messier with the Rangers.
"You can't fly off the handle when things aren't going well," says Taylor. "At the same time, you have to keep an even keel even when things are going real well."
Previous captain Dave Andreychuk retired last winter.
Clark is another not-so-big-name with a C. He replaces Jeff Halpern, who left for Dallas via free agency. Ollie Kolzig would be the captain but the rules disallow goaltenders because the league doesn't want goalies skating from the crease to the penalty box to debate referees' calls.
"Leadership is not a sometime thing or a come and go thing," GM George McPhee explained in picking Clark. "It is an all-the-time thing.
"Chris Clark has all-the-time leadership qualities. He is a leader in the mould of one of our all-time favourites, Dale Hunter, who was a quiet man off the ice, a cantankerous, ultra-competitive player on the ice."