The 49-year-old former footballer had two spells at the Stamford Bridge club - as a goalkeeper from 2006 until 2014, and later becoming a member of coaching staff - but he is now joining his former Chelsea head coach when Tuchel begins his managerial role on January 1.
Chelsea have not yet commented on the coach's departure, but sources have confirmed to Telegraph Sport that his decision to step down has already been made official.
Last month, Chelsea boss Enzo Maresca said he knew "one of the analysts" in his team had been approached by England and wouldn't stand in their way.
He said: "I know that one of them has been approached; one of the analysts.
"We are quite open for people to leave and take their chances in case they want to take it.
"We are open-minded in terms of allowing people to take chances and also we are happy to keep people who want to stay and if they want to go, they can go."
Before retiring from playing in 2014, Hilário made 39 appearances for Chelsea.
Antonio Conte brought him back in 2016 to be an assistant goalkeeping coach, and was promoted two years later by Maurizio Sarri.
Tuchel was announced as Gareth Southgate's replacement in October, and he is on an 18-month contract.