In 1931, now billed as Gene Raymond, he made his debut in "Personal Maid" beginning a string of roles in melodramas that often cast him opposite many of the screens notable females, to mixed results. In "Red Dust" (1932) he was Mary Astor's husband whose absence allows her to consummate an affair with Clark Gable. "Ex-Lady" (1933) effectively paired him with proto-feminist Bette Davis but "Brief Moment" (also 1933) saw him overshadowed by Carole Lombard. Raymond was the love interest for Delores Del Rio in the delightful "Flying Down to Rio" (1933) and he held his own opposite Joan Crawford in "Sadie McKee" (1934). After RKO put him under contract in 1935, he continued in the same vein in efforts like "The Bride Walks Out" (1935), with Barbara Stanwyck and "That Girl From Paris" (1937), alongside Ann Sothern. He offered delightful support to Robert Montgomery and Carole Lombard in Alfred Hitchcock's sole comedy "Mr. and Mrs. Smith" (1941). That same year, Raymond had his only screen pairing with his wife, singer-actress Jeanette MacDonald, in "Smilin' Through" (1941).

The outbreak of WWII interrupted Raymond's career as he chose to serve as a bomber pilot in the US Army Air Force. As tastes changed after the war, he found good roles scarce, turning instead to the emerging medium of television. Raymond served as host of and occasional performer on the NBC anthology series "Fireside Theater" (1949-55). The stage also provided an outlet, with the actor appearing in national tours of Broadway shows (i.e., "The Best Man" 1960) and summer stock (e.g., "Kiss Me, Kate"). His last film appearances were in "I'd Rather Be Rich" and "The Best Man" (both 1964). Raymond was a series regular, as an assistant to George Hamilton, in the short-lived adventure show "Paris 7000" (ABC, 1970).