Eton College will offer 12 free sixth form places to boys "with tremendous potential but limited opportunity".
The Orwell Award will be open to those who do not have the highest grades, recognising that their potential may have been limited by circumstances.
The places will be offered to Year 11 pupils at non-selective state schools and will cover full boarding fees.
Former prime minister David Cameron and Tory leadership hopeful Boris Johnson are among Eton's alumni.
Both the Duke of Cambridge and the Duke of Sussex were also pupils at the Berkshire school, which charges fees of more than £40,000 a year.
Headmaster Simon Henderson said the school had a tradition of offering free places "to deserving pupils" since it was founded in 1440, adding that there were more than 80 pupils currently in the school "who pay no fees"
"The Orwell Award will ensure that we continue this tradition by helping boys with tremendous potential but limited opportunity," said Mr Henderson.
"We are not targeting boys who will do well anyway.
"We're looking for applicants with vigour, talent and industry who, without proper support, will not be prepared for or even apply to the country's top universities."
The Orwell Award is named after Animal Farm author George Orwell, who was a scholarship pupil at Eton.
It is intended to give the recipients an educational experience they would not otherwise have been able to access.
Unlike previous scholarship programmes, it will assess applicants against specific criteria such as attending a school which Ofsted has identified as requiring improvement or which is in special measures.
It will also consider if a boy has refugee status, is in council care or foster case, if he is in the first generation of his family to go to university or if he has been in receipt of the pupil premium funding for disadvantaged students.
The announcement of the 12 sixth form scholarships comes at a time of increasing pressure on private schools and top universities to diversify their intake.