I'd have to give the nod to Lyndon Baines Johnson, President form 1963 - 1969. While George W. Bush is certainly known for No Child Left Behind, I believe history is going to give LBJ much more credit for being an education President.
There were two laws that really set LBJ apart. First, the Elementary and Secondary Education Act of 1965 gave large amounts of federal money to public schools for the first time (before, they had relied on state funding almost exclusively). Funding for school construction, extra teachers, aid to low income schools, free and reduced lunch programs were all a part of this act, which we still see affecting the schools today.
His second effort was the Higher Education Act of 1965, which created a large federal financial aid program to offer low-interest loans and scholarships to needy students. This has been periodically reauthorized by Congress again and again, most recently in 2008.
So in terms of lasting effects, I'd say LBJ was the most recent education President.