Alexander was also the country's first black member of Parliament, elected to the House of Commons in 1968 as the Progressive Conservative candidate for Hamilton West.
Lieutenant Governor David Onley made the announcement Friday morning.
"I am profoundly saddened to learn of the death of The Honourable Lincoln MacCauley Alexander, 24th lieutenant governor of Ontario," Onley said in a statement.
"Lincoln Alexander, known to all and sundry as 'Linc,' was a living legend in his hometown of Hamilton," he said.
Alexander's wife, Marni Beal, said he died peacefully at about 8:15 a.m. Friday.
"I've been sleeping beside him since he's been at the General," Beal told CBC Hamilton. "He was sleeping and the breath just went out of him."
Alexander will lie in state at Hamilton City Hall in the second floor foyer, outside council chambers, from Oct. 23 - 25.
Born in Toronto in 1922 to West Indian immigrants, Alexander served with the Royal Canadian Air Force during the Second World War, from 1942 until 1945.
He received a Bachelor of Arts at McMaster University in 1949 and graduated from Toronto's prestigious Osgoode Hall Law School in 1953. Alexander was appointed Queen's Counsel in 1965.
In 1968, he became Canada's first black MP and was re-elected in 1972, 1979 and 1980. He was the country's labour minister from 1979 to 1980 and served in the House of Commons until 1985.
That year, Alexander was appointed Ontario's 24th lieutenant governor. He held the post until 1991, focusing on youth and education.
Longest serving chancellor at University of Guelph
In 1992, Alexander was appointed a Companion of the Order of Canada and to the Order of Ontario.
After leaving office, Alexander went on to serve as chancellor of the University of Guelph, serving five terms as chancellor — the longest-serving in the school's history.
“At a time when racism was endemic in Canadian society, he broke through barriers that treated visible minorities as second-class citizens, strangers in their own land,” Onley said. “Lincoln Alexander's whole life was a rebuke to those who would equate ability with skin colour.”
Ontario Premier Dalton McGuinty said the country has lost a remarkable Ontarian and a great Canadian.
“Lincoln was a towering man, and his stature matched his influence,” McGuinty said in a statement. "Not just on all those fortunate enough to work with him, but all those who knew him. Indeed, he left an extraordinary legacy, both in his private life and as a public servant.”
“He broke down barriers. He made Ontario a better place for all of us, the next generation of public servants and citizens. “
Beal said Alexander will be lying in state at Queens Park.
His funeral service will take place at Copps Coliseum, she said.Suggest a correction