NCAN was incorporated as a 501(c)(3) nonprofit organization in 1995 by nine founding members that wanted to share best practices and spread college access and success services around the country. The founding members were:

• CollegeBound Foundation (Baltimore, MD)
• Cleveland Scholarship Program (now College Now Greater Cleveland)
• The Boston Plan for Excellence in The Public Schools Foundation (now uAspire)
• College Assistance Program of Dade County (Miami, FL) (now College Assistance Program, Inc.)
• I KNOW I CAN (Columbus, OH)
• Philadelphia Schools Collaborative (succeeded by Philadelphia Education Fund)
• Scholarship Fund of Alexandria (VA)
• Tidewater Scholarship Foundation (Norfolk, VA) (now Access College Foundation)
• The Winston-Salem Foundation (now Crosby Scholars Program)

NCAN held its first national conference in 1997, and in 2001 received a leadership gift from KnowledgeWorks Foundation to hire its first professional staff, based in Cleveland. In 2007, NCAN relocated to Washington, D.C., to raise its national profile and add policy change to its strategies.