The network, which follows a national summit on pupil disaffection, will be formed by a number of voluntary organisations with a proven track record of success with some of the most difficult pupils, such as Right Track, Barnardo's and the Aberlour Trust.
Peter Peacock accepted that there can be many reasons for pupils being turned off learning but said: "It is vital that we take action to re-engage these young people in learning and ensure that they don't miss out on the education opportunities available to them.
"The new network will share good practice between mainstream education and alternative providers to help meet the challenges we face in supporting disaffected pupils and their families, who are often living in difficult and trying circumstances."
The Pupil Inclusion Network Scotland will potentially involve more than 150 organisations that work with education authorities to support disaffected pupils. It will be able to call on pound;11 million from the Executive's funding for developing alternatives to exclusion.