Anthony, a tenor, died at his home in Tampa, Fla., from kidney failure following a long illness, Met spokesman Peter Clark said.
"Your talent, demeanor, joy and heart will be missed," mezzo-soprano Susanne Mentzer wrote on Twitter. "What a loss."
Beginning his career at the old Met on Broadway and moving uptown with the company to its new home at Lincoln Center for the Performing Arts in 1966, Anthony was a "comprimario," or supporting singer.
He shared the stage with the greatest classical artists of several eras, performing in the Met debuts of Marian Anderson, Birgit Nilsson, Jon Vickers, Leontyne Price, Franco Corelli, Joan Sutherland, Elisabeth Schwarzkopf and Jose Carreras.
"It's no exaggeration to say that Charlie Anthony is the soul of the Metropolitan Opera,