Born in rural Bowen, Mendoza Province, Zamora"s family moved to Santiago del Estero in 1968. He later became a leader in student politics, serving as President of the UCR student chapter Franja Morada at the Catholic University of Santiago del Estero and as President of the UCR"s youth wing for two terms. He became a lawyer and continued his political activities.
Elected to the Provincial Legislature in Santiago del Estero in 1991, he served in the post until 1993, and was elected Mayor of the city of Santiago del Estero in 1995.
He became a provincial deputy once again in 1997 and served as President of the UCR caucus until 1999. In that year he was elected vice-mayor of Santiago del Estero and took over as Mayor in 2001 when the incumbent resigned.
In 2003 he was elected Mayor of the city in his own right with 64% of the vote, serving until 2004. He was elected governor in 2005 on the Civic Front for Santiago ticket, with the support of some Peronists and Socialists as well as most Radicals (UCR) in the province.
From 2005 until 2007, Zamora"s vice-governor was Emilio Rached.
Rached was elected to the Argentine Senate in 2007, and later broke ranks with the governor. Zamora was re-elected governor in 2008 with 85% of the vote. Governor Zamora sought an amendment to the provincial constitution that would enable a third consecutive term.
The amendment was defeated in an October 22, 2013, Argentine Supreme Court ruling, however.
His alliance with Kirchnerists had by then led to his break with the UCR, which opted to endorse former Vice Governor Emilio Rached in a Progressive, Civic and Social Front ticket for the upcoming 2013 gubernatorial elections. Supported by President Cristina Fernández de Kirchner in a bid to broaden her support among "K" Radicals, Zamora was elected Provisional President of the Argentine Senate with the support of Kirchner"s majority Front for Victory caucus.
He took office on February 28, 2014.