Her parents were Juan Pío Montúfar, second Marquis of Selva Alegre, and aristocrat Josefa Teresa de Larrea y Villavicencio, who baptized her on 17 December of the same year.

In 1798, her father requested for her the benefits of a clause in Captain Manrique de Lara's will, which would favor a noble and poor girl with a large sum of money.

Although the girl belonged to one of the most important noble families of the then Real Audiencia de Quito, she was definitely not poor, however President Luis Muñoz y Guzmán assigned a part of her benefits to her.

[2] Montúfar was described as a distinguished lady, with a haughty bearing and luminous blue eyes, physical qualities to which added a determined character.

[2] Her careful education, the fruit of her father's enlightened thought, was reflected when she had to successfully take over family estates between 1809 and 1812.