Spaniard Benitez, 55, was relieved of his duties following a meeting of the club's board on Monday.
B team coach Zidane, 43, has been made first-team boss, but the length of his contract has not been made public.
The World Cup winner said: "I am going to put my heart and soul into this job so that everything works out well."
Benitez's final game was Sunday's 2-2 draw with Valencia, which left them third in La Liga, four points behind leaders Atletico Madrid.
Zidane, whose first game in charge will be on Saturday against Deportivo La Coruna at the Bernabeu, is the 11th coach to be appointed in Florentino Perez's 12 years as club president.
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'It's an emotional day'
Zidane thanked Perez for giving him the opportunity to train the "best club in the world with the best fanbase in the world".
The Frenchman added: "I want to do my very best to ensure that this club at the end of the season will have a trophy.
"It is an important day for me, it's an emotional day, even more emotional than the day I signed as a player for the club.
"I will be working hard with all the players and I think it will go well. I will put all the heart I have into this job for the club. Thank you very much."
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