Chára was drafted 56th overall by the New York Islanders in the 1996 NHL Entry Draft. After four seasons with the Islanders, he was traded to the Ottawa Senators during the 2001 NHL Entry Draft.
As a Senator for four years, Chára emerged as an elite defenseman in the league and more than doubled his previous offensive totals in his first season with Ottawa. In his second season with the team, 2002–03, Chára made his first All-Star Game appearance and recorded the second hardest shot behind Al MacInnis in the skills competition.
The next season, in addition to posting 16 goals and 41 points, Chára recorded the league’s third highest plus/minus, culminating into his first Norris Trophy nomination. Although he would lose to Scott Niedermayer as the league’s best defenseman, he would join Niedermayer on the NHL First All-Star Team.
After the 2004–05 NHL lockout, in which Chára played in the Swedish Elite League for Färjestad, he matched his previous NHL season’s 16-goal total and increased to 43 points, good enough for NHL Second All-Star Team honors.
On July 1, 2006, he signed a five-year, contract with the Boston Bruins and was named the team’s captain. He became only the third Slovakian-born NHL player to become a team captain. He was named to the 2007 All-Star Game, his second appearance, in Dallas and scored two goals in an 12–9 Eastern Conference loss. Chára also won the hardest shot segment of the preceding skills competition, clocking a shot at 100.4 mph.
In 2008, he was voted in as a starter in the All-Star Game for the first time in his career and repeated as the winner of the hardest shot competition, recording an even-faster 103.1 mph (166 km/h) on the radar gun. At the end of the season, Chára received his second nomination for the Norris Trophy after tallying a career-high 17 goals, 34 assists and 51 points, marking the fifth straight season he had either matched or increased his previous season’s points total.
In 2008–09, Chára was named to his fourth All-Star Game. As back-to-back champion of the hardest shot competition, Chára initiated a charity drive among the participants ($1,000 per player) to go to the charity of choice of the competition’s winner. Having raised $24,000 from the six competitors and their respective teams, the NHL and the NHLPA, Chára set a new Skills Competition record, with a 105.4 mph (169.7 km/h) slapshot. He donated the winnings to Right to Play. The shot passed Al Iafrate’s previous record-making 105.2 mph (169.3 km/h) slapper from just over a decade earlier.
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