McDermott, the most successful coach in Super League history having won eight major trophies during his eight-year stint in charge of Leeds, takes the reins from Shaun Wane, who stepped down in January.
The 56-year-old was chosen by a four-person panel comprising of ex-England players Kevin Sinfield and Kris Radlinski, plus Rugby Football League chair Nigel Wood and non-executive director Sara Symington.
McDermott, who represented both England and Great Britain during his playing career, said: "I'm incredibly proud to take on the role of England head coach ahead of the 2026 Rugby League World Cup.
"My focus now is on creating an environment where players can perform with confidence, represent the shirt with pride and give themselves the best chance of going deep into the tournament.
"I've always been hands-on and close to the detail, and that will be important in this role. My job now is to get the standards right, build belief in the group and make sure we're ready when it matters."
Currently based on the Gold Coast, McDermott will now prepare his brief for the World Cup in Australia, where three-time runners-up England start their campaign against Tonga on October 17.
The Yorkshireman edged out Leeds head coach and former Parramatta mentor Brad Arthur, Warrington's Sam Burgess, St Helens' Paul Rowley and Steve McNamara, who will take charge at Hull from next season, to land the role.
McDermott, who won four Super League grand finals as well as two Challenge Cups, the World Club Challenge and a League Leaders' Shield when at the helm of Leeds from 2010-2018, coached the USA at the 2017 World Cup and will decide on his England backroom set-up in due course.
Wood said: "We are delighted that Brian has accepted the role of England head coach, emerging from an outstanding field of candidates.
"The selection process was comprehensive, thorough and the RFL is indebted to all those that assisted in the process.
"As the most successful coach in Super League history, Brian has demonstrated his capability to build fine teams and his previous experience as an international coach also demonstrates his knowledge of the unique challenges of harnessing players from different clubs in an international setting.
"By working currently in the NRL, Brian will have day to day visibility of many of the opponents the England team will be up against, while he also has a great network around the Super League clubs to ensure that the England team have the best possible chances of success."
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