The CfBT Education Trust, formerly the Centre for British Teachers, already pays the chair about £20,000 a year, thanks to a previous ruling. Members of an operations board that reports to the trustees are also paid.
Neil McIntosh, chief executive of the trust, which has an annual income of more than £143m, said it would initially pay three trustees. "A minority of roles are more onerous and need some sort of pay," he said.
Charity law forbids trustees from receiving benefits without express authority from a clause in the governing document, from a court or from a Charity Commission ruling. Although charities occasionally pay trustees - usually their chairs - the vast majority remain voluntary. Some sector commentators think the CfBT case sets an important precedent.
"It's hugely significant," said Judith Rich, a governance expert. She said she believed the ruling would help large charities attract the kind of people they need. But she added: "Payment should be the exception, not the rule."
Stephen Bubb, chief executive of Acevo, said he knew of at least two more charities seeking to follow suit.
A Charity Commission spokeswoman said: "The commission considers requests on a case-by-case basis and was satisfied that the CfBT Education Trust met the criteria in our guidance."