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The 24-year-old Dutch driver took his 26th career win 0.9 of a second ahead of Spaniard Sainz, who closed the gap and set up a thrilling final chase thanks to a safety car deployment.
The Mexican's teammate Max Verstappen finished third to stretch his Formula One championship lead over Leclerc.
The win ahead of Mexican team mate Sergio Perez completed a hat-trick for Verstappen.
The victory was the Dutch driver's third of the season, and second in a row, and he made it happen with a crucial overtake around the outside on Sainz at the start to seize second place before blasting past Leclerc on the ninth of the 57 laps.
Verstappen has won at Imola for the second year in a row.
The Monegasque, who started from pole, crossed the line 5.5 seconds ahead of Spaniard Sainz.
Verstappen passed title rival Lewis Hamilton on the last lap. After a record 22 races, Verstappen had 395.5 points to Hamilton's 387.5.
The final race is in Abu Dhabi next weekend.
Verstappen finished second with Valtteri Bottas third for Mercedes after a controversial, roller-coaster weekend in Brazil.
Seven-time world champion Hamilton was second for Mercedes, holding off Red Bull's Sergio Perez who became the first Mexican to stand on his home podium.