Quinn ordered the freeze last week saying the legislature did not approve enough money for pay raises.
The union that represents state workers says it will go to court to fight the freeze.
Quinn holding his ground on the pay raise issue has stunned organized labor leaders around the state. Always considered a union friend, Quinn is putting at risk his Democratic Party's appeal to working men and women.
After Quinn announced 2,500 minimum wage Illinois Conservation Corps jobs for teenagers and young adults, the governor was asked again to explain why he cancelled the raises of 30,000 permanent state employees.
"The General Assembly chose not to appropriate money for these raises," said Quinn. "I have to follow the law. There is no choice that I had other than to follow the law."
By canceling the 2 percent pay increase, worth an estimated $77 million, the governor surprised and outraged many of his longtime supporters in organized labor.
"Harry Truman, the famous chief executive, said, 'The buck stops here," said Anders Lindall of the American Federation of State, County and Municipal Employees (AFSCME). "This sounds like trying to point the finger at someone else."
Lindall says AFSCME will take legal action to force the state to abide by the union contract.
"Pat Quinn is seeking simply to ignore the law and to walk away from a collective bargaining agreement," said Lindall.
Quinn's predecessor, Rod Blagojevich, signed the AFSCME contract in 2008. It was revised with union concessions twice during 2010 as Quinn ran for election.
Democratic State Rep. Ken Dunkin says his party's governor should not blame the general assembly.
"Throwin' us under the bus on this issue is just simply not fair," said Dunkin. "He made the agreement, it was his deal, and if we need to come back and address it, that's what we need to do."
The governor says that without enough money appropriated to pay the raises, his only plan, for now, is to defend his decision in court
"If they decide to sue, that's their right and we'll be happy to meet 'em in court, but if you look at the law of Illinois, it says over and over again: 'subject to appropriations'," said Quinn.
The union spokesman says AFSCME could file legal action to reinstate the pay raise as soon as Wednesday. Their contract does not expire until next year.
If the largest state employee union actively turns against the governor, it could have major political consequences for him.