Brooke died of natural causes at his Coral Gables, Florida, home, said Ralph Neas, Brooke's former chief counsel. Brooke was surrounded by his family.
Brooke was elected to the Senate from Massachusetts in 1966, becoming the first black to sit in that branch from any state since the post-Civil War Reconstruction era and one of nine blacks who have ever served there - including Barack Obama.
Brooke told The Associated Press he was "thankful to God" that he lived to see Obama's election as the first black U.S. president. And the president was on hand in October 2009 when Brooke was presented with the Congressional Gold Medal, the highest award Congress has to honor civilians. Obama hailed Brooke as "a man who's spent his life breaking barriers and bridging divides across this country."
"You could sense that this was a Senator of historic importance," McConnell said in a statement Saturday. "Indeed, he was."
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A Republican in a largely Democratic state, Brooke was one of Massachusetts' most popular political figures during most of his 12 years in the Senate.
Massachusetts Democratic Gov. Deval Patrick, the state's first black governor, remembered Brooke for his unselfish public service.
"He carried the added honor and burden of being 'the first' and did so with distinction and grace," Patrick said. "I have lost a friend and mentor. America has lost a superb example of selfless service."
However, late in his second term, Brooke divorced his wife of 31 years, Remigia, in a stormy proceeding that attracted national attention.