Guillen will now be allowed to pursue other managerial opportunities, with the Florida Marlins reported to be interested in hiring him.
"(The White Sox) gave me the opportunity to be free and do what's best for me and my family. I respect that," Guillen told reporters. "This is a decision I made for a lot of reasons. I have no regrets."
The White Sox picked up Guillen's 2012 contract option prior to this season, but he said in September that he would not return without an extension.
After meeting with White Sox Chairman Jerry Reinsdorf on Monday, Guillen told his players that the game against the Blue Jays would be his last.
The outspoken Guillen enjoyed a roller-coaster ride with the White Sox that included flare-ups with umpires, media and the front office. However, he will ultimately be remembered for his entertaining style and leading the franchise to its first championship in 88 years.
"We certainly cannot thank Ozzie enough for all he has done during his eight seasons as manager of the Chicago White Sox," Reinsdorf said in a statement.
"We shared the greatest moments together and wish him nothing but future success in baseball and in life."
(Writing by Jahmal Corner in Los Angeles; Editing by Peter Rutherford)