Maura's immediate family are conservative lawyers but they are part of the influential and aristocratic Maura dynasty, whose members frequently combine theatre and political high office. Her great great uncle was Antonio Maura (prime minister of Spain on five occasions and noted playwright), and three of her great uncles were Spanish cabinet ministers. Other relatives include a duke, a marquise, various minor nobles, a film director, and several writers.

Maura studied philosphy 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 appeared in the first film by Pedro Almodóvar, Pepi, Luci, Bom y otras chicas del montón, in 1980. They went on to collaborate on five additional films, the last of which was Women on The Verge of a Nervous Breakdown (1988), for which she was awarded the European Film Award "Felix" for best actress.

Maura and Almodóvar appear 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 is cited as a gay icon for the role of a transsexual she played in Almodóvar's La ley del deseo, strengthening her image as a strong woman who is never afraid to break through boundaries.