Perceval began a career in academia as a university professor and in public administration, co-ordinating projects for the provincial governments of Mendoza and Buenos Aires Provinces as well as the Argentine Chamber of Deputies.

[2] Perceval followed her early political mentor, José Bordón, and other left-wing Peronists into the FrePaSo coalition before the 1995 general election, but later returned to the Justicialist Party.

[2] She pursued a greater role for women in Senate committees historically chaired and dominated by men, and in 2007 become chairwoman of the Defense Committee;[1] in that capacity she became known for an unsuccessful effort in 2008 to rescind military courts martial in favor of civil trials, as she believed that courts martial deprive servicemen and women of due process.

[4] She also focused on the strengthening of democracy and democratic institutions, as well as promoting civil, political, social, cultural and economic human rights.

[3] Her appointment as Ambassador to the United Nations was approved unanimously by Congress, and she presented her credentials before the UN Secretary-General, Ban Ki-moon, on November 23, 2012.