The honor was given by the Public School Superintendents Association of Maryland.
In a statement released by Prince George's County, Maxwell said winning the award was "a thrilling and humbling experience."
Anne Arundel officials praised their former schools leader. "He and our entire organization have worked very hard to help propel our school system forward, and we are grateful for his seven years of service to our children," Anne Arundel County Board of Education President Teresa Milio Birge said.
Maxwell will represent Maryland in the National Superintendent of the Year Program sponsored by the American Association of School Administrators.
The Public School Superintendents Association of Maryland's membership includes superintendents from 24 school districts in the state. Maxwell is the group's immediate past president.
Maxwell stepped down as Anne Arundel's superintendent in June after seven years to take over in Prince George's, where he began his career and spent 22 years working as a teacher, principal and chief educational administrator.
Maxwell has been praised in Anne Arundel for launching magnet programs and multiple schools. He was named Educator of the Year in 2007 by the Maryland Parent Teacher Association.
Anne Arundel schools are currently led by interim Superintendent Mamie J. Perkins, who has a contract through the current school year. The Anne Arundel County Board of Education is in the process of selecting an outside firm to help in choosing a new superintendent.