On June 6, 1808, in the Valdepeñas uprising against Napoleon's troops, there was a lack of sufficient men to defend the village, so she encouraged women to go out and fight. Although Galán is usually depicted armed with a baton, one version has it that she smashed in the heads of the soldiers with her cast-iron stew-pan. The other women poured hot water through the windows and boiling hot oil on the road. This battle led, in part, to the French army abandoning the region of La Mancha, which in turn led to the decisive victory for the Spaniards at the Battle of Bailén. This town was granted the title of "Very heroic".
Galán married on May 2, 1810, to Bartolomé Ruiz de Lerma, from Valdepeñas, with whom she had two daughters. She died during her second daughter's birth on September 24, 1812, the same day La Mancha was released by the troops of Napoleon.