James joins from Dixons Carphone, Europe's leading specialist electrical and telecommunications retailer and services company, employing over 42,000 people in nine countries, where he is now Group Chief Executive since 2014, having been Chief Executive of Dixon Retail since 2012.
However the company trimmed its guidance for full-year profits, saying it will make a profit before tax of between £365m and £385m, down from a previous estimate of £360m to £400m.
"Together, I think that we can be very proud of the profound transformation that we have seen in Dixons Carphone and the sound footing, customer affection, and place in the world that it now enjoys".
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His exit is likely to be particularly poorly received because it will come just a fortnight after Humphrey Singer, his finance director, quit to take the same role at Marks & Spencer.
Chief executive Sebastian James has announced his departure in favour of Walgreens Boots Alliance, with Alex Baldock set to fill his shoes. The statement, coming a day ahead of schedule after current CEO James' notice of departure on Friday, echo the polarising Christmas period seen by United Kingdom retailers: Those with strong online presence (ex-ABF's Primark) enjoyed a record trading period, while those with a more traditional brick and mortar focus saw a continuing slide in sales.
As well as operating under the Carphone Warehouse name, Dixons Carphone also owns brands including Curry's, PC World and Team Knowhow.
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Sebastian James will step down after six years as CEO around the end of the company´s 2017-18 financial year in April, Dixons said in a statement.
He also will be contributing to the Group with involvement in a number of key areas, joining the company in the summer of 2018 and taking up his new role at the beginning of the new fiscal year on 1 September.
Nevertheless, Dixons warned that profits would be down sharply on past year, with consumers opting to keep their old handsets as opposed to upgrading to more expensive models.
December's fall in profits at Dixons Carphone was attributed to mobile phone operations and changing customer behaviour, with consumers inclined to hold on to their existing handsets for longer, Mr James said.
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"The consumer's OK in the United Kingdom, in our European businesses the consumer is very strong", he said.