Barclays is offering 3,000 work experience placements for pupils - but only for students attending the academies and free schools championed by Michael Gove.
The "package of support" from the bank is part of a new relationship with the Department for Education, which will also see senior staff members at the company encouraged to sit on the governing bodies of the state-funded schools.
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 £1.25m fund created by the bank.
Although no one from the DfE was available to comment on why only certain schools were to be included in the programme, a spokesman from Barclays said: "We asked the DfE which area would benefit most from our support and they recommended free schools and academies."
The measures were unsurprisingly welcomed by the education secretary Michael Gove.
"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 the bank was "delighted" to be part of the programme.
"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."
But Melissa Benn, education campaigner, who has openly opposed the government's education policies, said the move "confirms the suspicion of many who think that this government is only interested - indeed, obsessed - with free schools and academies.
"It is working hard, yet again, to secure advantages for these schools at the expense of other elements of school estate."
Gove and his Whitehall officials have been scrutinised in recent months after The Huffington Post UK revealed staff at the DfE had sent business emails from private accounts, with one putting a school under pressure to convert to academy status.
"While all work experience placements are to be welcomed," Benn continued, "There is always the worry that too close a tie between business and schools undermines the most important element of education, the acquisition of knowledge and fostering of a genuine love of learning."
Gove added: "I want a new generation of businesses to work together with schools. Thanks to the Barclays package, students, teachers and governors will benefit enormously."
Barclays currently has a £15m programme offering help in financial literacy education, or money skills, in schools and the wider community, which will also be expanded to target free schools and academies.
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 at the free schools and academies.
"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."
Christine Blower, general secretary of the National Union of Teachers said opening schools up to the market place is "simply wrong".
“Children and young people should not be influenced at an impressionable age by whichever large company manages to gain a foothold in their school.
“Schools in deprived areas whose pupils do not fit the right socio-economic profile will not get the help, financial or otherwise, from business.
“Removing schools from the democratically accountable expertise and support that local authorities provide is a disastrous move. While becoming a golden goose for big business, Michael Gove’s academies and free schools policy is utterly undermining the principle of a fair education for all."