Kane's ad began airing statewide Monday, the same day the two candidates squared off for their only scheduled debate, campaign spokesman Josh Morrow said Tuesday.
In the 30-second spot, the narrator calls Kane "a prosecutor, not a politician" and says she'll "clean up the corruption in Harrisburg."
A spokesman for Freed's campaign said Tuesday that it plans to make "a robust ad purchase" this week.
"We're looking forward to introducing Dave Freed to the electorate. We expect a spirited remaining two weeks of the race," said the spokesman, Tim Kelly.
Kane, who worked as a Lackawanna County prosecutor for more than 12 years, relied heavily on TV advertising to elevate her name recognition and attack her primary opponent, former U.S. Rep. Patrick Murphy, in her victorious campaign last spring.
Freed, Cumberland County's elected district attorney, was unopposed for the GOP nomination. He has not previously aired TV ads in his campaign for attorney general.
In Monday night's debate at Widener University Law School in Harrisburg, Kane described herself as politically independent and suggested Freed used his political connections to lock up the nomination.