Free schools and academies in England are to be offered 3,000 work experience placements for pupils with Barclays under a new package of support announced by the bank.
Groups could also be eligible for £5,000 in grants to help pay for research and plan bids to set up free schools from a £1.25 million fund created by the bank.
The measures were welcomed by Education Secretary Michael Gove, who said he hoped other companies would follow the example set by Barclays.
"I am sure that Barclays will be, as it were, the leader of the pack, the centre forward in a team effort that will see other companies that we will be talking about in weeks and months to come, pitching in to try and help the fantastic work that is going on in state education at the moment," he said.
Antony Jenkins, Barclays chief executive of retail and business banking, said they were "delighted" to be part of the programme.
He said: "We really do believe in the power of education to create social mobility, to create powerful effects in people's lives and to create economic growth, which of course is important to us as a bank."
Other measures announced by Barclays include encouraging senior staff members to sit on governing bodies of state-funded schools including academies and free schools.
A £15 million programme offering help in financial literacy education, or money skills, in schools and the wider community run by Barclays will also be expanded to target free schools and academies.
Mr Jenkins said the announcement was part of the bank's wider work in education.
"Barclays is a non-political organisation. We are happy to support this initiative - we think it is going to have a lot of impact - but it is not the only thing we are doing in the educational space by any means," he said.
He said the work experience placements would be targeted at 16 to 18-year-olds.
"We take our responsibilities in this area very seriously, so we don't just want people to come in and tidy up the photocopying room or make coffee for people," he said.
"We want them to truly have an experience of what it is like in the world of work."
Mr Gove and Mr Jenkins launched the scheme at Westminster Academy in north west London, described as a "fantastic" school by the Education Secretary.
The pair met pupils from Year 8 taking part in a money skills lesson helped by volunteers from Barclays.