The Liberace biopic, shown on the cable network HBO in the US, won three awards including best TV movie and a best actor award for Michael Douglas.
Breaking Bad was named best drama, while Modern Family took the leading comedy award for the fourth time.
Claire Danes took the best actress prize for her role in Homeland.
Accepting his first ever Emmy award, Michael Douglas thanked his family and his wife, Catherine Zeta Jones.
Catherine Zeta Jones and Michael Douglas, who have been married for 13 years, announced last month that they were “taking time apart”.
Michael Douglas also thanked his co-star, fellow nominee Matt Damon.
“You’re magnificent,” he said.
The actor added: “The only reason I’m standing here is because of you.”
It was the second consecutive Primetime Emmy award win for Claire Danes in the leading actress category for her portrayal of troubled CIA officer Carrie Mathison in Homeland.
Claire Danes paid tribute to Henry Brommell, one of the writers of the critically acclaimed series, who died in March and received a writing award posthumously during the ceremony.
Her co-star, British actor Damian Lewis lost out in the lead actor category to Jeff Daniels, who was the surprise winner for his role in The Newsroom.
It was the first ever Emmy nomination and win for Jeff Daniels, who plays self-righteous news anchor Will McAvoy.
Jeff Daniels beat stiff competition from Kevin Spacey, nominated for House of Cards, Mad Men‘s Jon Hamm and Breaking Bad actor Bryan Cranston, who was widely tipped to take the coveted accolade.
As well as taking the top honor of best drama series, Breaking Bad was also successful in the supporting actress category, with Anna Gunn winning ahead of Downton Abbey‘s Maggie Smith and Mad Men‘s Elisabeth Moss.
Anna Gunn, who plays Skyler White in the hit show, dedicated the win to her daughters.
Best supporting actor in a drama series went to Bobby Cannavale for Boardwalk Empire.
British screenwriter Abi Morgan had success with newsroom drama The Hour, claiming the award for best writer in the mini-series or movie category.
In the best comedy actress category, Julia Louis-Dreyfus won her fourth Emmy for her role as the US vice-president in Veep, from The Thick Of It creator Armando Iannucci. She also won an Emmy for Veep last year.
“This is so much good fortune it’s almost too much to bear,” said Julia Louis-Dreyfus.
“I’m very grateful to have the opportunity to make people laugh. It’s a joyful way to make a living.”
Jim Parsons of The Big Bang Theory won his third Emmy for best actor in a comedy.
Jim Parsons, who plays Sheldon Cooper in the CBS comedy, scored the hat trick after previous wins in 2010 and 2011.
Toby Jones and Imelda Staunton had each been up for best actor and supporting actress for Hitchcock drama The Girl while Charlotte Rampling had been nominated for Restless for best supporting actress in a TV movie.
The glittering ceremony included a performance by Elton John, who paid tribute to the late pianist Liberace.
Elton John, who performed Home Again, said he was “honored” to have been asked to take part in the ceremony for the first time in its 64-year history.
Among those to receive a special posthumous tribute was 31-year-old Cory Monteith, who died in July of a drug and alcohol overdose.
His Glee co-star Jane Lynch described him as a “beautiful soul”.
“He was not perfect, which so many of us here tonight can relate to. His death is a tragic reminder of the rapacious, senseless destruction that is brought on by addiction,” she said.
The Sopranos star James Gandolfini was also honored during the ceremony.
James Gandolfini, who won three Emmys for his role as a therapy-seeking mob boss in the show, died in June following a heart attack.
Tributes were also paid to producer Gary David Goldberg, Jean Stapleton and Jonathan Winters.
Despite being nominated for 17 awards, American Horror Story: Asylum won just one accolade, while the hotly tipped Netflix drama, House of Cards, also took one award for best directing in a drama series for David Fincher.
US cable and satellite television network HBO led this year’s awards, winning seven Emmys, followed by Showtime with four, ABC and NBC with three each and AMC and Comedy Central with two each.
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