Despite leading Belgium to the quarter-finals of the World Cup, Garcia left his position after the tournament, mutually agreeing not to extend his contract.
Former AC Milan and Barcelona midfielder Van Bommel quickly emerged as the most likely replacement, and has now been officially announced.
“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," he 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 Belgium after previously coaching Antwerp from 2022 to 2024 in what was a hugely successful spell.
In his first season there, he led the club to their first league title since 1957 and their first-ever double, with them also claiming the Belgian Cup. He then followed that up by winning the club their first Super Cup at the start of the following campaign before leading them to the cup final again.
He didn't extend his contract at the end of that second season, which had been hindered by financial difficulties and differences of opinion between himself and the board, and has since spent the past two years focusing on assisting with the development and injury recovery of his son, PSV player Ruben.
He's now returning to the touchline to lead Belgium for an initial two years, with his contract expiring at the end of Euro 2028, and he'll be assisted by former Netherlands teammate Boudewijn Zenden and former Belgium international and AZ manager Maarten Martens.
“I am truly delighted that Mark van Bommel and his assistants have agreed to take on this challenge," said Vincent Mannaert, the sporting director of the Belgian FA.
"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.”