In a setback for England boss Steve Borthwick, the highly-regarded Walters is set to quit the Red Rose set-up ahead of November internationals against New Zealand, Australia, South Africa and Japan.
The Welshman will replace Jason Cowman, who left Ireland after their Six Nations title triumph earlier this year, in Andy Farrell's coaching staff.
Ireland head coach Farrell, whose side also face the All Blacks and the Wallabies in November, as well as taking on Argentina and Fiji, said: "We are delighted that Aled has agreed to join the Ireland team.
"He has a wealth of experience and has been a key part of many successful environments over the course of his career to date."
Walters joined England from Leicester ahead of the 2023 Rugby World Cup in France, having been involved in the Springboks' 2019 World Cup triumph, having previously worked at Irish province Munster.
England head coach Borthwick said: "Aled is an excellent coach and has worked hard to help develop the current squad over the past 12 months.
"He leaves with our very best wishes for the future."
Walters added: "The Ireland team has gone from strength to strength in recent years and it's an exciting time to rejoin Irish rugby as the team looks to achieve more success in the years to come.
"I've made some great memories coaching England, and I want to thank Steve, the management team and the players for their friendship and support. I wish the squad every success for the future."
