Graham Thorpe will take over the role in time for the one-day side's tour of New Zealand next month.
A statement from England Cricket Board managing director Hugh Morris read: "Graham Gooch is going to focus now on Test cricket.
"We would like to focus on that area of the game. We've got back-to-back Ashes series coming up and a five-Test series against India in 2014.
"That's an enormous amount of very high-profile Test cricket and Graham will be focusing his attention on working one-on-one with our Test players."
The coaching shift is the latest attempt by the ECB to reshuffle their management structure following the appointment of Ashley Giles as limited overs coach in November.