There has been speculation of a possible deal between the parties since Italy was plunged into uncertainty after the March 4th vote resulted in a hung parliament with no group in a position to govern alone.
"There is no Five Star-led government that can win the confidence of the PD," Renzi, who resigned as PD head after the party's devastating defeat in the polls, said in an interview with newspaper Corriere della Sera.
The maverick Five Star Movement (M5S), became Italy's leading single party on election night with 32.7 percent of the vote. Should the PD refuse to help it govern, M5S could be forced to ally with the far-right League party, an option both parties have so far refused to consider.
Renzi also dismissed the idea of an agreement with the League and its right-wing coalition, which won 37 percent of the vote.
"We will not be used as a crutch by anyone and we will stay where the citizens have put us: in opposition," he said.
Matteo Renzi pictured during his resignation speech. Photo: Alberto Pizzoli/AFP
The former prime minister stepped down as party secretary after PD slumped to just 18.7 percent of the vote. The centre-left party is due to meet Monday afternoon to begin the process of choosing Renzi's successor.
Several of the party's leaders have spoken out in agreement with Renzi, refusing any alliance with M5S, but a handful of party members have defended a deal with the populists.
Italian President Sergio Mattarella, who will begin coalition talks with the parties in early April, last week called on political leaders to show "responsibility".
His message was immediately interpreted by the local media as an invitation for the PD to make a deal with M5S.
"Calls for accountability are always useful, but they are addressed to the largest groups in parliament," Renzi said, adding that it is up to the election's winners to try to form a government. The M5S and the right-wing coalition led by League chief Matteo Salvini have "the right and perhaps even the duty to try," he said.
"The nationalists have the same agenda on vaccines, Europe, immigration, taxes, bureaucracy. Let them form a government if they can."