The NCAA filed the lawsuit in Harrisburg federal court Wednesday, hours after Gov. Tom Corbett signed the legislation into law.
The complaint said the Pennsylvania Institution of Higher Education Monetary Penalty Endowment Act is unconstitutional.
Corbett sued the NCAA in federal court last month, saying a set of penalties imposed against Penn State over its handling of the Sandusky scandal should be thrown out on antitrust grounds.
State and congressional lawmakers had objected to use of the NCAA fine to finance child-abuse prevention efforts in other states.
Corbett's general counsel's office hasn’t commented.