Born in Watertown, New York State, he worked as radio announcer, first at high school, and then continuing afterwards. He moved to the West Coast and trained as an actor at the Pasadena Playhouse. When short of money he decided to do club acts so that he would get the cash at the end of the evening.

This was the start of a new career, and by 1952 he was doing stand-up comic routines at the Cabaret Concert in Sunset Boulevard, Los Angeles. In 1954 at Club LaVie in Altadena he performed his first female impression using a stole, a boa, and a hat. His impersonation acts were at first mainly in gay clubs on the US West Coast and in Florida. He particularly made his name with the gay audience at San Francisco's Gilded Cage club.

He did not regard the padding, the costumes, and make-up as the key to his performance, but rather it was accurate acting that he aimed for and was proud of. In fact, in some states it was illegal to cross dress, for example in Florida where he played in the Echo Club in Miami in the early 1960s. In these circumstances, instead of full drag he performed with props such as a silk scarf, a cigarette holder, and a hat. Charles always rejected the sobriquet "female impersonator", vehemently, insisting that he was instead a "male actress".

His fame spread and he went onto the international cabaret circuit. In the 1970s he played at Country Cousins in Chelsea. His imitations included Tallulah Bankhead, Carol Channing, Joan Crawford, Bette Davis, and Mae West.

In 1974 he started his one-man show in New York to rave reviews. He brought the show to the Fortune Theatre in London in 1975. During the late 1970s and 1980s he was often a guest on television shows, including Fame, LaVerne, and Shirley and Love. He was also frequent guest on television chat shows. In 1988 he played the part of the drag queen Bertha Venation in the film version of Harvey Fierstein's play Torch Song Trilogy and he was briefly shown doing his Bette Davis impersonation.

After Bette Davis died in 1989 Charles Pierce, then in his sixties, revived his act with a show called Fasten Your Seatbelts, and he became a star again. He died aged 72, in Los Angeles.