In order to take up the role James has left his position as Dixons Carphone CEO, a position he has held since 2014.
James will join the Walgreens Boots Alliance this summer before taking up his new positions at the beginning of the new fiscal year on September 1.
Elizabeth Fagan, who has led Boots since June 2016, will continue working with the company and will take on the newly created role of non-executive chairman also in the new fiscal year.
Commenting on his appointment, James said: “I am very excited to be joining Walgreens Boots Alliance at this time in its history, and to have been offered the privilege of leading Boots, surely one of the UK’s most iconic, venerable and trusted brands.
“At a time of unprecedented change in both the retail and healthcare markets, to build on the fantastic work that the team have done over the last few years, and to be a part of the next chapter for this great company is an extraordinary opportunity. I look forward to getting to know my new colleagues at both Boots and WBA in the next few months.”
Alex Gourlay, co-chief operating officer for Walgreens Boots Alliance, added: “We are delighted that Sebastian will join our Company at an equally exciting and challenging time for the retail environment in the UK and for the future development of Boots, a brand synonymous with pharmacy and care.
“We are sure his deep retail expertise will drive significant progress and innovation at Boots for the benefit all our stakeholders.”