"We must not tolerate failing schools," Richard Riley said in a policy speech in the southern city of Atlanta. "This should be our great patriotic cause - our national mission."
Mr Riley's declaration follows President Clinton's pledge of $51 billion to help to make American schools "the envy of the world" after decades of decline in many areas.
Mr Clinton pledged in his State of the Union speech that education would be the number one priority of his second term, and has called for the same level of bipartisan resolve that characterised the Cold War.
"There are schools that should not be called schools at all," said Mr Riley. "They have done just about everything to kill the sense of wonder in their students. And then we wonder why truancy increases and young people drop out."
Mr Riley, a grandfather of eight, said American's past willingness to tolerate such schools was a symbol of low educational expectations.
Now, he added: "We need to stop making excuses and get on with the business of fixing our schools. If a school is bad and can't be changed, reconstitute it or close it down. If a principal is slow to get the message, find strength in a new leader. If teachers are burnt out, counsel them to improve or leave the profession."
If necessary, Mr Riley and other educational officials said, laws and teacher contracts that have traditionally frustrated efforts at reform should be rewritten, making it easier to revamp radically those schools where students did not learn and drop-out rates were high.
Mr Riley said the problems were not necessarily limited to a small number of failing schools, but afflicted an entire system that had not kept up with the times.
"Astronomers probe the unfolding majesty of the universe, even as scientists race to map the genetic make-up of humanity," he said. "Yet we struggle to put the old industrial model of education behind us.
"We need to stop dumbing down our children and reach up and set higher expectations. Our children are smarter than we think."