On 4 February 1945, Chalbaud married General Marcos Pérez Jiménez, and was First Lady of Venezuela during his presidency between 2 December 1952 and 23 January 1958.

During the presidency of Pérez Jiménez, she was best known in the national media for her role at official diplomatic events in which she presided or took part with the formal name "Doña Flor de María Chalbaud-Cardona de Pérez-Jiménez".

The goal of the organization was to "guarantee by all means possible the assistance of Venezuelan mothers and children, and to dedicate itself to other types of social security."

Between 1953 and 1954, the organization began endeavors around the country such as kindergartens, schools, playgrounds and maternal centers.

[3] Chalbaud remained with Pérez Jiménez during his trials on embezzlement charges in the 1960s and his years of exile in Spain, until he died in Alcobendas.