Carmen Melendez, who became the South American country's first female admiral a year ago, takes over the defense ministry from Diego Molero. Until Friday, she was serving as minister in the office of the president.
"Here, where the remains of our commander lie, I have decided to name a new military high command," President Nicolas Maduro said in a speech carried live on all local TV networks.
"I've decided to name a woman to head the defense ministry for the first time: Carmen Melendez, soldier of the fatherland."
Maduro narrowly won a presidential election in April after his mentor Chavez died following a two-year battle with cancer.
Friday's armed forces reshuffle was long expected as Maduro consolidates his position atop the diverse leftist coalition built by Chavez that ranges from military officers and socialist ideologues to businessmen and armed militants.
Melendez played a prominent role in Chavez's administration. In October he gave her a broad mandate to carry out inspections of government departments and public works to investigate claims of inefficiency and corruption.
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