Grizzard died Tuesday at New York-Presbyterian/Weill Cornell Medical Center of complications from lung cancer, said his agent, Clifford Stevens.
Grizzard's film roles included a bullying U.S. senator in "Advise and Consent" in 1962 and an oilman in "Comes a Horseman" in 1978. On television, Grizzard made regular appearances on "Law & Order" and won a best supporting actor Emmy for the 1980 TV movie "The Oldest Living Graduate," which starred Henry Fonda. His TV credits stretch back to the '50s, when he appeared in various anthology series such as "Playhouse 90."
But he considered himself primarily a stage actor.
He had made his Broadway debut in 1955 as Paul Newman's brother and fellow convict in "The Desperate Hours." He was nominated for Tonys for "The Disenchanted" in 1959 and "Big Fish, Little Fish" in 1961.
"When we were on the stage together, he was the best thing around," Newman said.
Among his other credits were Neil Simon's 1976 "California Suite," a 1975 revival of "The Royal Family" and the 2001 drama "Judgment at Nuremberg."
With Albee, Grizzard appeared in the original 1962 production of "Who's Afraid of Virginia Woolf?" and won a Tony more than 30 years later in 1996 for his performance in a revival of a 1967 play, "A Delicate Balance."
"It's wonderful to get a pat on the back every now and then," said Grizzard when he won.
In Albee's Pulitzer Prize-winning "A Delicate Balance," a wealthy suburban couple have their home invaded by two frightened friends, who never say what they are afraid of. Grizzard played the husband, Tobias, in the revival.
"Grizzard, as Tobias, personifies the ineffectual peacemaker, a man with a good heart who learns that even charity is not enough," The Associated Press drama critic Michael Kuchwara wrote in his review.
"Grizzard rises to the play's shattering climax, in which his idea of friendship is shattered."
In a 1996 AP interview, Grizzard said he drew on his own fears as an actor to play the role. "Fear is a universal motivator. ... I think the only time I really get mean or angry or contentious is when I'm frightened."
"Who's Afraid of Virginia Woolf?," a searing portrait of marital strife, caused a sensation when it opened in 1962. Grizzard played Nick, the young husband who, along with his wife, is victimized by the older warring couple, George and Martha. (George Segal played Nick in Mike Nichols' acclaimed 1966 film version.)
During rehearsals, Grizzard didn't realize the play was going to be such a big hit, he recalled in 1996.
"Then it was like wildfire - the reaction from people and the crowds clamoring to get in. It was startling. 'Virginia Woolf' was such a brilliant play on so many levels. It made people's minds go wild."
Grizzard stayed with "Virginia Woolf" for only three months, leaving to play Hamlet in the inaugural production of the Guthrie Theater in Minneapolis in 1963. He also played other career-stretching roles there over the years, in such plays as "Henry V," "The Three Sisters," "Volpone" and "Saint Joan."
Grizzard was born in Roanoke Rapids, N.C., but grew up largely in Washington. He attended the University of North Carolina and worked at an ad agency before getting involved in the theater, appearing at the Arena Stage in Washington.
He is survived by his partner, William Tynan.