Ukrainian President Volodymyr Zelensky hailed the move as "historic", after signing the letter of intent with his French counterpart Emmanuel Macron at an air base near Paris.
Deliveries of the Rafale F4s are planned to be completed by 2035, while the joint production of interceptor drones is starting this year.
"This is a strategic agreement which will last for 10 years starting from the next year," Zelensky said at a joint briefing with Macron on Monday.
Ukraine will also get "very strong French radars", eight air defence systems and other advanced weaponry, he added.
Zelensky stressed that using such advanced systems "means protecting someone's life... this is very important".
Russia has in recent months increased its drone and missile attacks on Ukraine, targeting energy and rail infrastructure and causing massive blackouts across the country.
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