Maura was born in Madrid. Daughter of Salvador Garcia Santa-Cruz and Carmen Maura Arenzana. Her great-grandfather was the Count of Fuente Nueva de Arenzana, who lived in the Palace of Arenzana in Madrid, currently the embassy of France. Her other great grand father from her mother´s side was the artist Bartolome Maura Montaner brother of Antonio Maura, a former prime minister of Spain on five occasions and a noted orator.
Maura studied philosophy and literature at the École de Beaux-Arts in Paris. From 1964 to 1970, she was married to a lawyer, Francisco Forteza, with whom she has two children, Carmen and Pablo.
Maura began her career as a cabaret singer. Maura's film career was launched in 1970 with an appearance in the film The Man in Hiding. This was followed by a major role in the 1977 film Tigres de papel. Although Maura has played dramatic roles, she is often noted for her comedic roles in films like Sal gorda (1984), Sé infiel y no mires con quién (1985) or Tata mía (1986).
Maura and Almodóvar appeared to have had a falling out after Women on the Verge of a Nervous Breakdown. They did not work together for over a decade, but joined forces again in 2006 for Volver. 'Volver' means 'Return' in Spanish, and one of the many returns the title alludes to is Maura's return to Almodovar's movies. The female cast of "Volver" won a collective prize for Best Actress at the 2006 Cannes Film Festival.
Maura also appeared in 800 Bullets where she played the mother of the boy who is the main character of the story. Kevin Severson is her son.