The rocket blasted off into overcast skies at 5:57 am (0857 GMT) from Europe's spaceport in Kourou, French Guiana, on the northeastern coast of South America.
A little under two hours after the launch, the satellites separated from the rocket and were released into low-Earth orbit in stages.
Applause rang out at the Guiana Space Centre after all 32 satellites were successfully deployed, an AFP correspondent reported.
It was the second Ariane 6 launch carrying 32 satellites for Amazon Leo, the internet constellation of the giant US company founded by American billionaire Jeff Bezos.
The launch was the seventh Ariane 6 flight, and just the second using four boosters -- its most powerful configuration.
Similar to fellow billionaire Musk's Starlink, the Amazon Leo constellation aims to provide a reliable internet connection for customers in areas without an existing network.
To do so, Amazon Leo plans to initially deploy 3,200 satellites into low-Earth orbit -- however, there have been delays.
There are currently just 239 in space, including some launched by the rival SpaceX company of fellow billionaire Musk, according to data provided to AFP on Wednesday by Look Up, a French startup specialising in space surveillance.
In March, Starlink crossed the symbolic threshold of 10,000 satellites -- and now has 10,162 in orbit, the startup added.
The French company Arianespace, which operates the rocket, will carry out a total of 18 launches for Amazon Leo, its main commercial customer.
Amazon Leo has become crucial for keeping Europe's relatively new Ariane 6 rocket competitive, because many European commercial customers have opted to rely on reusable SpaceX rockets for launches.
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