The Rhinos prop will retire from rugby league at the end of the current season after 10 years with the Headingley club.
Peacock has won eight Super League Grand Finals and has made more than 500 appearances for Leeds, Bradford, Yorkshire, England and Great Britain.
Peacock said: “I have had a great time at Leeds and learnt so much about how the club is run from top to bottom.
“The Rhinos are a blueprint for a successful sporting business and the challenge for me now is to take those lessons and try and implement my own thoughts in a new environment.
“Hull KR are a club with huge potential within a city that is rugby league mad and having invested wisely in their facilities in recent years. I know a number of people over there already and I am looking forward to working with Chris Chester, Willie Poching, Mike Smith and Neil Hudgell in my new role.
“Whenever we have gone over there to play, it is clear Rovers have a fanatical supporter base. I think it is vital that you have a hard core of good people who want the club to succeed to be able to build and plan for development in the future.
“Now that I have the next chapter of my career finalised, I am fully focused on finishing my time with Leeds as strongly as possible and leaving my home town club in the best possible position.”