Oct 18: Benzema scored 44 goals in 46 games as he helped Real win the Champions League and La Liga in 2021-22.
Lionel Messi (seven) and Cristiano Ronaldo (five) had won the award on 12 of the previous 13 occasions.
Bayern Munich's Sadio Mane, who was at Liverpool in 2021-22, was second ahead of Manchester City's Kevin de Bruyne.
Barcelona's Alexia Putellas retained the Women's Ballon d'Or, awarded to the best best female footballer of 2022.
England Euro 2022 winner and Arsenal forward Beth Mead was second.
Premier League champions Manchester City, who had six nominees at the ceremony, were awarded Club of the Year ahead of Liverpool.
The Ballon d'Or is awarded to the best footballer of the year, based on performance over the 2021-22 season.
First Frenchman to win prize since 1998
Monday's ceremony in Paris saw French F1 driver Esteban Ocon arrive at the Theatre du Chatelet with the Ballon d'Or trophy in a racing car.
Benzema is the first Frenchman to win the prestigious award since Zinedine Zidane in 1998. Zidane was at the event to present his countryman with the prize.
"This prize in front of me makes me really proud," said Benzema. "When I was small, it was a childhood dream, I never gave up. Anything is possible.
"I'm really proud of my journey here. It wasn't easy, it was a difficult time for my family as well."
Benzema was the overwhelming favourite to win this year's award.
His 44 goals included a hat-trick in 17 second-half minutes against Paris Saint-Germain in the Champions League, and another away to Chelsea in the quarter-final first leg.
He also scored three more goals over two legs of the semi-final against Manchester City.
The 34-year-old, who has been at Real Madrid since 2009, is expected to play a key role for France at the World Cup in Qatar which starts on 20 November.
The Ballon d'Or is voted for by 100 journalists from around the world.
Five-time winner Ronaldo ranked 20th
Messi and Ronaldo have dominated the award in recent years, apart from in 2018 when Croatia midfielder Luka Modric won it.
Messi had already won the trophy more times than any other player and his seventh success in 2021 came after wins in 2009, 2010, 2011, 2012, 2015 and 2019.
However, he was not nominated this time after an underwhelming first season at Paris St-Germain.
Manchester United's Ronaldo, who last won it in 2017, was placed 20th of the 30 players nominated, the Portuguese's lowest Ballon d'Or ranking since 2005.
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