The south London side confirmed the 39-year-old has signed a contract with the club until the summer of 2016.
Luzon, who oversaw Israel U21’s win 1-0 over England at the 2013 U21 European Championships in Israel, was most recently in charge of Belgian side Standard Liege, and will link up with the current Israeli captain Tal Ben Haim at the Valley.
He told Charlton’s website: “I am happy to have joined Charlton and will work as hard as I can to try and make the club successful.
“We have talented players in the squad and it is my job to try and bring the best out of them.
“It is important to have a positive spirit in the team and I want to ensure the entire group is fighting together for the good of the club. I look forward to taking training for the first time and getting my ideas across to the players.”
Charlton owner Roland Duchâtelet said: “I think the appointment of Guy Luzon will prove to be a very good one for the club. I regard him as an extremely talented coach who has already achieved a lot in his career so far. There were a lot of records broken during his first season at Standard Liège and they had the best defensive record in the league. He is a passionate coach who will give his all to Charlton and I hope supporters will get behind him.”
Luzon’s first game in charge of the Addicks will be on Saturday when then travel to Watford.