He completed his studies at the Colegio Carolino, and took part in the movement for independence from the very beginning.

He was named Governor of Valparaíso and when General Bernardo O'Higgins was elected Supreme Director, he appointed Zenteno as Secretary of War and Navy where he distinguished himself by his activity.

In 1822, after retiring from the ministry of war, he was appointed political and military governor of Valparaiso, and promoted to brigadier.

In 1831 he was appointed inspector-general of the army, and from 1833 till 1846 he filled several important offices in the war department, and was also a member of the supreme council of war, the Society of agriculture, and was several times elected to congress representing Santiago and later, Victoria, and serving as vice-president of the chamber of deputies.

He was one of the founders and first editor of the El Mercurio of Valparaíso, taught law at the Universidad de Chile and was a member of the martial court (military tribunal).