Napolitano's Democratic party has a majority in Italy's House but the People of Freedom, headed by Berlusconi, has control of the Senate, Italy's ANSA news agency reported.
Berlusconi, a three-time former prime minister, initially reached out to Democratic party head Pier Luigi Bersani to form a broad alliance but Bersani refused.
Berlusconi then moved to Napolitano, saying that if the two parties worked together, lawmakers could begin tackling Italy's economic problems.
"We have to find a way to give life to a coalition government, in the country's interests," Berlusconi said Friday. "We are willing to meet with the other political forces to hammer out the urgent measures needed to tackle the extremely difficult economic situation."
However, PD Senate Whip Luigi Zanda reiterated Bersani's refusal, stating that the Democratic party and Berlusconi's People of Freedom party were "light-years apart."