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Police arrested jeweller Mineo, 80, and at least 45 others in Sicily just before he was due to be officially anointed at a reconvened Mafia Commission or Cupola, the police said.
The suspects are accused of extortion, illegal gun possession, arson, Mafia association and other crimes, investigators said.
The Sicilian Mafia managed to rebuild the Cupola after it had not met for years, Italian media reported.
The Cupola met in May for the first time since 1993 and was due to appoint Mineo official heir to notorious Mafia boss Toto Riina who died in prison last year.
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Police also arrested three other Cupola members in the swoop. The four senior Mafia leaders had all recently served prison time for their activities.
Italian media reported that police obtained crucial information by tapping the phone of one of the senior arrested members, Francesco Colletti.
He reportedly told his driver about details of the May 29 Cupola meeting, describing it as "a beautiful meeting, very serious, with country people, old people."
It remains a mystery where the Cupola meeting took place, but Colletti's conversation with his driver implicated Mineo and others.
Colletti reportedly rejoiced in the resurrected Cupola, which was to be an improvement on Riina's "tyranny".
"We all got up and kissed," Colletti reportedly said of the end of the meeting.
Coded messages
Lifelong Mafia member Mineo was arrested as part of investigations by judge and prosecutor Giovanni Falcone in 1984 and imprisoned for five years.
Falcone was murdered in a massive car bombing in 1992. Mineo was rearrested in 2006 and imprisoned for another 11 years.
Mineo survived a 1992 ambush that killed his brother Giuseppe, around six months after another brother, Antonino, was murdered outside the family jewellery shop.
Italian police in March arrested 11 suspected gangsters accused of aiding and abetting senior mob fugitive Matteo Messina Denaro.
Hunted by police since 1993, Denaro, 56, was also considered to be a successor to Riina and fellow boss Bernardo Provenzano, who also died recently in prison.
A former Cosa Nostra hitman, Denaro has been sentenced in absentia to life in prison for multiple murders.
The only photo of him dates back to the beginning of the 1990s.
Over the past two decades Italian police have increased arrests and seizures targeting his entourage, in a bid to isolate the notorious boss.
In 2015, police discovered that Denaro had abandoned modern methods of communication and was giving orders to his men via traditional "pizzini": small bits of paper containing encoded messages.
Italian media reported that Mineo was a preferable new Mafia leader because he was not in hiding.