The Britain’s Got Talent hosts, who arrived for the awards ceremony by private jet straight from filming in Cardiff, also scooped the Best Entertainment Programme award for I’m A Celebrity, Get Me Out Of Here.
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As if that wasn't enough, the presenting duo won a special surprise landmark award, presented by Philip Schofield with a message from Prince Charles. "The nation has taken them to their hearts," the royal said of the popular pair.
"Words can't describe how we feel tonight," said Ant McPartlin backstage.
"We genuinely had no idea this was going to happen; didn't have a clue our mams had been flown down and had their makeup done and done an interview."
Meanwhile, Best Serial Drama Performance went to Coronation Street's Julie Hesmondhalgh.
A recent storyline involved her character Hayley Cropper's diagnosis with terminal cancer and a harrowing scene in which she committed suicide with her devoted husband Roy by her side, watched by a whopping 10.6 million.
The actress took her on-screen hubby on stage to pick up the award. She told the audience: "We said that if either of us were lucky enough to get this tonight, we'd come up together because there ain't no Hayley without Roy and there ain't no Roy without Hayley."
Corrie also beat rivals EastEnders, Emmerdale and Hollyoaks to win Best Soap for the third year.
This Morning was been named Best Daytime Show for the fourth year in a row, while Sherlock star Benedict Cumberbatch scooped an award in the new category Best TV Detective. Doctor Who won Best Drama, and Best Drama Performance went to former Time Lord, Matt Smith.
Strictly Come Dancing took home the Best Talent Show trophy for the second time, beating ratings rivals X Factor, Britain's Got Talent, Dancing on Ice and The Voice UK.
Winners of the National Television Awards 2014:
- Factual Entertainment – Paul O’Grady: For the Love of Dogs
- Entertainment Programme – I’m A Celebrity…Get Me Out Of Here
- Documentary Series – Educating Yorkshire
- Newcomer – Khali Best
- Drama Performance – Matt Smith
- Daytime – This Morning
- Comedy – Mrs Brown’s Boys
- Serial Drama Performance – Julie Hesmondhalgh (Coronation Street)
- TV Detective – Benedict Cumberbatch
- Entertainment Presenter – Ant & Dec
- Drama – Doctor Who
- Serial Drama – Coronation Street
- Landmark Award – Ant & Dec
- Talent Show – Strictly Come Dancing