"Well, crap. I didn't expect this. I never win," Daniels quipped, adding the exception was when the American Association for Retired People gave him an "Over 50" acting prize a few years ago for his work in "The Squid and the Whale."
"This is better," he declared.
Daniels beat out the critics' favorite, "Breaking Bad" leading man Bryan Cranston, for the honor.
Earlier in the evening, Cranston's co-star Anna Gunn won the statuette for Outstanding Supporting Actress in a Drama. Gunn plays Skyler White, the wife of Cranston's terminally ill drug dealer Walter, on the series, which is wrapping up its last season.
Claire Danes won the Emmy for Outstanding Lead Actress in a Drama Series for her performance as a bipolar CIA agent in "Homeland."
Bobby Cannavale won the award for Outstanding Supporting Actor in a Drama for his portrayal of a 1930s-era gangster "Boardwalk Empire."