The daughter of singers Dorival Caymmi and Stella Maris (Adelaide Tostes Caymmi), Nana Caymmi is nevertheless an established singer on her own, as corroborated by her extensive discography and two gold records. Also a composer, she has been recorded by giants such as Milton Nascimento.

Nana debuted on record in Dorival Caymmi's album Acalanto (Odeon, 1961). Marrying a Venezuelan doctor, she moved there in 1959. Her love for boleros came from this period. Seven years later, with two children, pregnant, and divorced from her husband, she came back to Rio in June 1966. There, she became involved with the Tropicalia people (her brother Dori, already a producer for Philips, was in close contact with all members of the movement, but neither of the two joined it). In this period, she met Gilberto Gil on the weekly TV Excelsior show Ensaio Geral, recorded in São Paulo, on which Maria Bethânia, Marília Medalha, Tuca, Francis Hime, Toquinho, Sérgio Ricardo, Ciro Monteiro, and the Tamba Trio also regularly participated. Caymmi started an affair with Gil, and eventually they became informally married, which was a general scandal, as she was white and he was Black. At the I FIC (International Song Festival), in Rio in 1966, with a newborn son waiting backstage, she presented "Saveiros" (Dori Caymmi/Nelson Motta), winning first place amidst booing, as some people preferred the timid interpretation of a novice Gal Costa of Gil's song "Minha Senhora" (written with Torquato Neto). She would only find out afterward, but even Gil himself took part in the booing. At the III FMPB (Brazilian Popular Music Festival, presented by TV Record at the Teatro Paramount, São Paulo), she sang with Gil "Bom-Dia" (written by the two).

A period of ostracism followed: she didn't fit into the pop scene of Tropicalia, with its preference for iê-iê-iê; the other movement that could attract her, due to its respect for Brazilian culture, was the canção de protesto ("protest songs") during the military dictatorship. The movement, gathering people as diverse as the sambista do morro carioca (from the Carioca hills) Zé Keti, the Northeast Brazilian João do Vale, the bourgeois Nara Leão, and many others, was proscribed by Caymmi, who thought the canções de protesto as boring, full of enormous lyrics and ugly melodies. So, her shows were always a failure during that period. She survived by singing in Portuguese in nightclubs in Argentina, Uruguay, and Chile. Among her several solo albums deserving mention are Nana Caymmi (1979), Voz e Suor (with César Camargo Mariano; 1983), Chora Brasileira (1985), Caymmi's Grandes Amigos (1986), Talento de Nana Caymmi (1987), and Só Louco (recorded live at the Montreux Festival in 1989 with Wagner Tiso), all through EMI. In 1983, Caymmi appeared in the documentary Bahia de Todos os Sambas, recorded in Rome.

In 1994, she was included in the Songbook Edu Lobo (Lumiar). Her album Bolero sold more than 100,000 copies and brought Caymmi her first gold record. She was included on a posthumous tribute to singer Clara Nunes, Clara com Vida (EMI, 1995), a record that sold 96,000 copies in four months. In that same year, Caymmi was awarded by APCA as the Best Female Singer of the Year. In 1996, she released Alma Serena, and in 1997, No Coração do Rio. She was again awarded by APCA as the Best Female Singer of the Year in 1998. Her 1999 album Resposta ao Vento, after having been included in the soundtrack of TV Globo soap opera Hilda Furacão, sold 100,000 copies, her second gold record. In 2000, she released another solo set, Sangre de Mi Alma, singing boleros and other compositions, including "Noel Rosa." ~ Alvaro Neder, Rovi