María Esther Ballivián grew up in an artistic environment. Her paternal grandmother, Elisa Rocha de Ballivián (1865-1966) founded La Paz’s first private painting academy in in 1905. Her father was a lawyer and diplomat, and the family lived in several countries beginning when she was quite young. In 1941-1942 she began taking painting lessons with the American artist Robert Ades (1911-1984). In 1945, when the family moved to Peru, she attended the Escuela Nacional de Bellas Artes in Lima. Upon her return to Bolivia, she studied at the studio of the painter Juan Rimsa (1903-1978).
In early 1950 M. E. Ballivián spent her afternoons painting with the artists Graciela Rodo (born 1935) and Norah Beltrán (1929-2016). This was when she made the oil painting Madre e hijo [Mother and child, 1952], an example of her so-called blue period.

In 1954 she moved to Santiago, Chile, where she began learning printmaking. There she travelled in social circles where she met personalities and intellectuals such as Salvador Allende and Pablo Neruda. She also made oil paintings in the Cubist mode, such as Carreta [Cart, 1957].

During her stay in Chile, M. E. Ballivián trained at Taller 99, a studio run by the painter Nemesio Antúnez (1918-1993) where many artists worked on printmaking techniques. In 1957 she was awarded a grant to continue her studies in Paris, and attended Atelier 17, the studio led by the famous printmaker Stanley William Hayter (1901-1988). She also frequented the Académie de la Grande Chaumière, where she met Henri Goetz (1909-1989), and later studied at his private studio. While in France her painting style turn toward abstraction. An example of that is Abstracto [Abstract, 1959]. In 1960 she returned to live in Bolivia, but in 1963 returned to Paris for a year to sharpen her skills.

In 1966 she received a fellowship to study metal engraving at the Museu de Arte Moderna de Rio de Janeiro. The painting Abstracto [Abstract, 1968] was made during her stay there. Upon returning to Bolivia, she became a teacher and workshop director at the Centro Cultural Brasil-Bolivia, and starting in 1967 taught printing and painting at the Facultad de Arquitectura de la Universidad Mayor de San Andrés. In the early 1970s M. E. Ballivián became head of that university’s visual arts department.

In 1973, she abandoned Abstract Expressionism and began painting subtle and slightly gauzy female nudes, as can be seen in her 1976 work Recostada [Allongée].

She took part in many exhibitions in Bolivia and abroad during her lifetime, and received several prizes, such as the Gran Premio Pedro Domingo Murillo in 1960.

M. E. Ballivián died suddenly in 1977, but, thanks to her family, her work is still in circulation. It has been featured in several posthumous exhibitions and publications, including a book about her life and art written by her daughter, Marie France Perrin.