Announcing the first 750 schools to join the pilot scheme, the Department for Education said breakfast clubs had "an important role to play in the government's commitment to remove the stain of child poverty".
Education Secretary Phillipson said: "Free breakfast clubs are at the heart of our Plan for Change, making working parents' lives easier and more affordable, while breaking down barriers to opportunity for every child."
Reacting to the upcoming launch of the scheme, shadow education minister Neil O'Brien said the Conservative government supported more than 2,000 schools through its national school breakfast club programme and he criticised Labour for scrapping planned reforms to child benefit.
''Children and their families deserve better," he added.
Devon tops the list with 25 schools in the programme, followed by England's largest local authority, Birmingham, with 24.
Both Wales and Scotland have programmes to provide free breakfasts to children in some primary schools.
Guidance sent to schools taking part in the pilot scheme says they will receive a set-up payment to cover equipment and material.
Under the scheme, schools will then be reimbursed by the government based on attendance at the clubs - a school with 50% participation in the pilot scheme could get £23,000 a year, the government said.