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Renzi, who met Napolitano for 90 minutes, will need to seal a formal coalition deal with the small center-right NCD party to secure a governing majority and name his cabinet before seeking a formal vote of confidence in parliament later this week.
Brief profile of Matteo Renzi according to the BBC
Matteo Renzi is just 39 years old and has never been a member of parliament. Now he has brought down Prime Minister and party rival Enrico Letta, calling for a new government in an address from PD headquarters. He is now widely expected to be Italy's next leader.
The young party leader is sometimes called Il Rottamatore ("The Scrapper"). The nickname refers to his call to scrap the entire Italian political establishment, which is widely regarded as discredited, tainted by corruption, and as having failed the nation decade after decade.
His rise has been seen as a sign of much-needed generational change, and he enjoys by far the highest approval rating of any politician in the country. He is, in his own words, "hugely ambitious".
Mr Renzi presents himself as a break with the past in every way, BBC Rome correspondent Alan Johnston reports.
It's a contradiction in terms to say 'You should have spoken to [Forza Italia] but not to Berlusconi. Should I have spoken to [his fiancee's dog?]”Matteo Renzi
He exudes a restless energy. He likes to pace the stage in black jeans and attends meetings in shirt sleeves. He travels around either in a small car or on a bicycle.
He is relaxed and easy - fast and fluent as he speaks without notes, ranging across Italy's many problems, and offering broad-brush solutions.Restoring belief
He always seeks to instil a belief that politics can be done differently, that change is possible.
He once finished a televised debate by saying he would offer something very rare in Italy: "Hope."
"People are weary and disillusioned," he said. "They don't believe anymore. I believe, and that's why I do politics - because I still believe."
Winning control of the PD is a major step on what Mr Renzi hopes is a journey to the prime ministerial palace.