Under the deal, announced by Education Secretary Michael Gove, bank staff will sit on governing boards, provide financial advice to schools and offer work experience opportunities to pupils.
The Barclays Money Skills education programme will be offered to free schools and academies, while teachers and other school staff will have access to online business skills training materials.
Free schools and academies will also be offered free banking accounts with the bank.
Christine Blower, NUT general secretary, 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.
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