Álvarez was born in a small town in Jalisco, but moved to Mexico City with her father when her parents separated around 1906. For a decade, she lived with her father in a large mansion, but upon his death was taken in by her older half-brother, who sent her to boarding school. After completing a traditional education, in 1922 she enrolled in the Escuela Nacional Preparatoria, where she met her lifelong friend, Frida Kahlo. A friendship with another of her childhood friends, Manuel Álvarez Bravo, blossomed into romance around the same time and the two married in 1925. Her husband taught her photography, as well as development techniques, and for nearly a decade, she acted as his assistant. As she sought to explore her own creativity and was unhappy in the marriage, the couple separated in 1934.