Garcia guided Belgium to the quarter-finals of the tournament before both parties agreed not to extend his contract, opening the door for Van Bommel to take over.
The former Netherlands midfielder said he was proud to be given the opportunity to lead one of Europe's strongest national teams.
"It is a great honour to become head coach of Belgium. I would like to thank the Royal Belgian Football Association for their confidence in me," Van Bommel said.
"Belgium has outstanding players and enormous potential. Together with my coaching staff, we want to build a team that is disciplined, ambitious and brave enough to compete with the very best.
"Success is never guaranteed, but hard work, honesty and commitment are. We will give everything to help this team improve every day and make the Belgian people proud.
"I am looking forward to meeting the players, the staff and the supporters, and beginning this new chapter together."
Van Bommel returns to Belgian football after a highly successful spell with Antwerp between 2022 and 2024. During his first season, he guided the club to their first Belgian league title since 1957 and completed a historic league and Belgian Cup double. He also led Antwerp to the Belgian Super Cup and another domestic cup final before leaving at the end of his second season.
Since then, the 49-year-old has spent time away from management, helping his son Ruben, a PSV player, with his development and recovery from injury.
Van Bommel has signed a two-year contract that will run until the end of Euro 2028. He will be joined by former Netherlands teammate Boudewijn Zenden and former Belgium international Maarten Martens as part of his coaching staff.
Belgian FA sporting director Vincent Mannaert believes the new coaching team has the experience and ambition to help the Red Devils move forward.
"I am truly delighted that Mark van Bommel and his assistants have agreed to take on this challenge," Mannaert said.
"They are highly motivated and ambitious, and I am convinced that, with their international experience as both coaches and players, they will be perfectly placed to help our Belgian Red Devils continue to improve, achieve results and reach their full potential, both individually and as a team."
Belgium will now look to build on their World Cup campaign under Van Bommel as preparations begin for the Euro 2028 qualifiers.
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