The five colleges will be checking on each other's progress as they all attempt to progress from good to excellent.
Mini-inspections of each other's work will form part of the attempt to improve student success at Burton college, City college Coventry, Burnley college, Gloucestershire college of art and technology and Grimsby college.
Keith Norris, principal of Burton college, said they would visit the other colleges to test their self-assessments, in a scaled down version of the new Ofsted inspection regime.
"We will use each other to get an external view of our progress," he said.
"It's only a surprise that we haven't done it before. In many ways, the best way to improve standards and students' experience is to work together.
"Coming together to form a group to achieve excellence is sending a message that the people who care most about student success are colleges, principals and staff, not external bodies."
The "excellence group" was formed after Burton college held a seminar outlining its own publicly stated aim to match the performance of the top 10 per cent of colleges.
Governors had committed the college to the target, but insisted that it should not be achieved at the expense of no longer catering for students of all abilities and interests.
Several other principals asked Burton to lead a network to support others with the same ambitions. Mr Norris said: "Even senior managers were saying, 'This is high risk to announce it publicly.' They asked. 'Are we not setting ourselves up to fail?'"
He also hopes that the group can provide a voice for improving colleges.
"Our main aim is to make sure we move to excellence, not to be a pressure group," Mr Norris said.
"But, if things happen which make it more difficult for colleges to operate, then we will say so."