Henry, 39, finished his glittering playing career in 2014 with New York Red Bulls after previously starring for Monaco, Juventus, Arsenal and Barcelona.
He left the latter role in July because Gunners boss Arsene Wenger did not want Henry juggling his coaching with his punditry.
“He is someone who knows how to develop a collective mentality, how to work together to win,” said Martinez.
“He won the World Cup in 1998 and has the experience to achieve great things.”
Henry was not present at the press conference as Martinez announced his first squad since becoming coach.
Belgium face Spain in a friendly next Thursday and then take on Cyprus away in their opening qualifier for the 2018 World Cup on September 6. The Guardian