All eyes will be on the duo as they aim to continue their winning streak, in their first public appearance since Ant McPartlin revealed he is splitting from his wife.
McPartlin and Declan Donnelly are up against presenting duo Holly Willoughby and Phillip Schofield and Bradley Walsh for the coveted TV Presenter title at the awards, held at the O2 London.
The Geordie duo are reigning champions, having won the title for a record-breaking 16 years, and bookies have tipped them to succeed again, with William Hill offering odds of 1/10 that they will take the title.
McPartlin recently announced his divorce from wife Lisa after 11 years, following months of speculation about their relationship.
Earlier in January, he said he was "very sad" to confirm the news, which came months after a stint in rehab for a two-year addiction to super-strength painkillers following a knee operation in 2015.
McPartlin returned to work on the new series of Britain's Got Talent last week along with Donnelly, but the NTAs - broadcast live on ITV - mark the first major public appearance for the TV star.
The ceremony, fronted by returning host Dermot O'Leary, will see many stars of the small screen vying for accolades in categories such as Crime Drama, Talent Show, Serial Drama, Comedy and Newcomer.
The drama gong looks too close to call with infidelity potboiler Doctor Foster and date rape drama Liar up against medical stalwarts Call The Midwife and Casualty, as well as fantasy series Game Of Thrones, which will be hoping to take the prize home to Westeros.
The Great British Bake Off will be vying for the Challenge Show trophy after its move from the BBC to Channel 4, but faces tough competition from I'm A Celebrity... Get Me Out Of Here, MasterChef and Love Island.
This year the awards will also pay tribute to the late Sir Bruce Forsyth by naming a major prize after him.
Ant & Dec's Saturday Night Takeaway, The Graham Norton Show, Celebrity Juice and All Round To Mrs Brown's will compete for the inaugural Bruce Forsyth Entertainment Award.
The National Television Awards ceremony will be broadcast on Tuesday January 23 at 7.30pm on ITV.