The army arrived in December 1810 at Potosí. Del Valle's participation in the battles of "Huaqui (20 June 1811) and the army's subsequent retreat to Jujuy, the exodus from Jujuy (23 August 1812), the victories at Tucumán (24 September 1812) and Salta (20 February 1813), and the defeats at Vilcapugio (1 October 1813) and Ayohuma (14 November 1813)" were recorded. Prior to the Battle of Tucumán, she sought permission from General Manuel Belgrano to tend the troops who had fallen in the front lines. Belgrano denied permission, on the grounds that women were not suited for duty at the front. Ignoring his order, del Valle proceeded with her plan and was later recognized by Belgrano with the rank of captain in the army. During the Battle of Ayohuma, del Valle wounded when she was shot by the enemy and taken as prisoner by the Spanish forces. During her captivity, she assisted several prisoners in escapes and was sentenced to be publicly flogged for nine consecutive days. She eventually escaped and returned to the army to assist with the battlefield wounded, remaining through the end of the conflict.