Lilli Palmer made her film debut in the low-budget mystery drama movie ‘Crime Unlimited’ in 1935. She played the role of a jewel thief who seduces a policeman to fall in love with her. The following year, she acted in Alfred Hitchcock's ‘Secret Agent’. In the late 1930s, she appeared as a femme fatale in the films ‘Silent Barriers’ (1937) and ‘The Man with 100 Faces’ (1938).
Many war movies were made in the 1940s, and Palmer starred in several of them, including ‘Thunder Rock’ (1942), in which she appeared alongside Michael Redgrave, who played an anti-fascist journalist who retreats to Canada. She co-starred with her husband, actor Rex Harrison, in the film ‘Notorious Gentleman’ in 1945. This marked her first collaboration with him. The next couple of years saw her appearing in the spy film ‘Cloak and Dagger’ (1946), co-starring with popular actor Gary Cooper, and the noir sports drama ‘Body and Soul’ (1947), in which her male lead was John Garfield.
In the 1950s, she and her husband became a popular duo in the theater. In the early 1950s, they appeared together in the Broadway plays ‘Bell, Book and Candle’ (1950), ‘Venus Observed’ (1952), and ‘The Love of Four Colonels’ (1953). Their joint movie appearances included the crime thriller ‘The Long Dark Hall’ (1951) and the comedy-drama ‘The Four Poster’ (1952). Lilli received the Venice Film Festival Award for this performance. She hosted her own TV show, ‘The Lilli Palmer Show,’ in 1951.
In 1956, Lilli Palmer played the role of Anna Anderson in ‘The Story of Anastasia.’ She won the Deutscher Filmpreis for Best Actress for this role. She portrayed a teacher opposite Romy Schneider in the German film ‘Mädchen in Uniform’ in 1958. She shared screen space with Fred Astaire and Debbie Reynolds in ‘The Pleasure of His Company’ in 1961. The next year, she played the character of Frau Marianne Möllendorf opposite William Holden’s Eric Erickson in ‘The Counterfeit Traitor,’ an espionage thriller based on real events.
In 1963, she appeared in another true Second World War story, Disney's ‘Miracle of the White Stallions.’ In her later career, she was more active on TV. She played Mrs. Frank in a TV production of ‘The Diary of Anne Frank’ in 1967 and starred as Manouche Roget in the six-part TV drama series ‘The Zoo Gang’ in 1974. One of her last roles was in the acclaimed TV miniseries ‘Peter the Great’ in 1986.