Safi, whose real name was Wadih Francis, helped spread colloquial Lebanese Arabic outside his country, becoming known to many Arabs as "the man with the golden voice."
During a career that spanned seven decades he worked with a string of legendary Arab composers and singers such as Egypt's late Mohammed Abdul-Wahhab, the late Syrian-Egyptian Farid al-Atrash and Lebanon's Fayrouz.
The state-run National News Agency said Saturday Safi fell ill while staying with his son, Tony, the night before. He was immediately rushed to a nearby hospital where he died late Friday.
"His passing is a loss to the nation and every Lebanese home," President Michel Suleiman said in a statement Saturday. "He embodied the nation through his art."
The Professional Musicians Syndicate called on Suleiman and outgoing Prime Minister Najib Mikati to declare a day of national mourning to mark Safi's death. Mikati posted on his Twitter account that he was "lucky to have lived during an age Wadi Safi left his mark upon."
The son of a policeman and the second of eight siblings, Safi was born in the mountain village of Niha. He lived in near poverty in the village until his family moved to Beirut when he was nine.
There, he enrolled in a Catholic school and began singing with its choir.
When he turned 17, his elder brother Toufic showed him an announcement about a signing competition at state-run Lebanon Radio. He placed first out of 40 contestants and began working at the station.
He later travelled to Brazil where he spent some years before returning to Lebanon.
Safi left Lebanon at the start of the 1975-90 civil war, travelling first to Egypt, then Britain and finally France.
Nostalgia-loaded "Lebanon you are a piece of the sky" and "We are coming" about Lebanese migrants were among his many hits.
Syria's state-run news agency SANA described Safi as "the giant of Arab singing."
In addition to Lebanese, Safi held Egyptian, Brazilian and French citizenship. His funeral will be held at Beirut's Saint Georges Cathedral on Monday, according to NNA. Safi is survived by his wife, Melfina Francis, and six sons and daughters.