But Carme Chacon, 37, the outgoing housing minister seen as a rising star in the ruling Socialist Party, was named to head the defence ministry, the first woman to hold the position.
She succeeds Jose Antonio Alonso, who last month was named speaker of the lower house of parliament.
There were nine women and eight men in the new cabinet.
During his re-election campaign, Zapatero had vowed to "eradicate sexism, harassment and intolerance".
During his first four-year term, his government had already passed a raft of liberal social reforms, such as laws to allow same-sex marriages, promote gender equality, combat domestic violence and make divorce easier.
The new government included five new names, while four other ministers were ousted, including Jesus Caldera, outgoing labour minister, a close ally of Zapatero.
Among the new faces were Bibiana Aido, 31, the equality minister and Cristina Garmendia, the science and innovation minister, 45.
Earlier on Saturday, Zapatero took the oath of office in front of King Juan Carlos in a brief ceremony at the royal Zarazuela Palace, following his Socialist Party's election on March 9.
Zapatero has identified the flagging economy and the fight against the armed Basque separatist group ETA as his main challenges.
Solbes will have the key task of implementing an economic stimulus package.
The former EU economic commissioner is viewed as a financial disciplinarian. During the prime minister's first mandate, he was able to turn in budget surpluses for several years running, something rare in Europe.
The Spanish prime minister has appealed for
cross-party support [AFP]
But he must now open the purse strings, as Zapatero has promised to dip into the budget surplus to pay for public works schemes and increase the minimum wage.
The Bank of Spain predicts the economy will grow by 2.4 percent this year, its lowest rate in over a decade and after expanding 3.8 per cent in 2007, as the global credit crunch and rising interest rates hit Spain's once-buoyant construction industry.
"We must continue to boost the economy and do it in a new way, less dependent on construction," Zapatero said while announcing his government.
Zapatero has also appealed for a cross-party strategy to combat ETA, which has killed 822 people in its nearly 40-year campaign for an independent Basque nation encompassing parts of northern Spain and southwestern France.
Zapatero's first four-year term was marked by confrontation with the conservative opposition Popular Party over his failed attempt to negotiate peace with ETA.
Spanish lawmakers on Friday confirmed Zapatero as prime minister for a second term.
He received the backing of all 169 Socialist deputies, while 158 legislators voted against him and 23 abstained.
The Socialists were seven seats short of an absolute majority in the 350-member lower house of parliament.
The prime minister on Friday acknowledged he did not have a clear majority in parliament, but that "many scenarios are possible" in order to achieve the necessary support to pass legislation.