Born in Warsaw, Lempicka briefly moved to Saint Petersburg where she married a prominent Polish lawyer, then travelled to Paris. She studied painting with Maurice Denis and André Lhote. Her style was a blend of late, refined cubism and the neoclassical style, particularly inspired by the work of Jean-Dominique Ingres. She was an active participant in the artistic and social life of Paris between the Wars. In 1928 she became the mistress of Baron Raoul Kuffner, a wealthy art collector from the former Austro-Hungarian Empire. After the death of his wife in 1933, the Baron married Lempicka in 1934, and thereafter she became known in the press as "The Baroness with a Brush".
Following the outbreak of World War II in 1939, she and her husband moved to the United States and she painted celebrity portraits, as well as still lifes and, in the 1960s, some abstract paintings. Her work was out of fashion after World War II, but made a comeback in the late 1960s, with the rediscovery of Art Deco. She moved to Mexico in 1974, where she died in 1980.