The move by Paul, who was elected last year with backing from the Tea Party, halted debate in the Health, Education, Labor and Pensions Committee Wednesday, The Washington Post reported.
Paul said the review of the bill has been rushed.
"This process is rotten from the top to the bottom," said Paul, who has introduced 74 of the 144 amendments proposed for the bill. "I would ask that we have a hearing; let's find out what we think of No Child Left Behind before we rush through a 868-page bill that no one has time to read. This is what's wrong with Washington."
The Senate rule he invoked stipulates no committee can meet without unanimous consent once the Senate has been in session two hours.
Sen. Tom Harkin, D-Iowa, the committee's chairman, pledged to resume committee debate on the bill quickly.
Harkin, who had worked for more than a year with the ranking Republican, Mike Enzi of Wyoming, to overhaul the No Child law, pointed out the committee had 10 hearings on the bill last year.
"We had hearings with superintendents, teachers, principals, broad input from across America," Harkin said. "Does that mean every two years we have to start from scratch every time?"
Last month, President Barack Obama told Education Secretary Arne Duncan to waive the requirements of the law for states that embrace the administration's education policies. The Post said at least 39 states, along with the District of Columbia and Puerto Rico, plan to apply for a waiver.