New ministers of information and communication, agriculture, the environment and indigenous peoples were also sworn in.
In the swearing-in ceremony aired on state television, Chavez called on his new ministers to continue "the fight to transform the old capitalist and bourgeoisie state ... into a socialist state."
He also called for greater government efficiency.
Chavez won 55 percent of the vote in the election, beating Capriles by 11 percentage points. Chavez has been in power for almost 14 years and his new term is for six more years.