The rugby league legend was amongst the star-studded crowd at London's O2 as his film, 'Rob Burrow: Living with MND', was in the running for one of the top prizes.
It saw Rob and his wife Lindsey allow cameras into their Pontefract home last year to show the realities of life with the debilitating disease.
The 30-minute film was shortlisted alongside documentaries about Deborah James, a pioneering campaigner who was diagnosed with incurable cancer, the singer Lewis Capaldi, and Matt Willis, a musician who has fought against addiction.
‘Lewis Capaldi: How I’m Feeling Now’ took home the award.
But despite missing out on the prize, Rob's film has still raised a huge amount of awareness about MND, which he was diagnosed with in 2019. The former scrum-half has also raised a huge amount of money for charities.
They include the Leeds Hospitals Charity, which wants to build a specialist, state-of-the-art MND centre in the city.
Many were moved by emotional scenes of Rob's former teammate Kevin Sinfield carrying him over the finish line at the inaugural Leeds Marathon that was named after him earlier this year.
Rob's wife, Lindsey, a physiotherapist and tireless campaigner, raised £110,000 for charity by running the same marathon.
She told the Yorkshire Evening Post that letting cameras into their home with kids Macy, Maya and Jackson was a daunting prospect, but it was with the knowledge of her husband's passion for raising awareness that she agreed.
Prior to tonight's ceremony, she said: "I can't think of anyone more deserving than Rob to win this award. He has opened his doors to show the world the brutality of MND and what it's like living with it at a time when he's at his most vulnerable. To do that is really brave and courageous.
"He has given people so much hope. He's just an all-round selfless, special person."
The National Television Awards is the only big awards show of its kind in which the winners are chosen by a public vote. It is considered to be one of the biggest nights in television of the year, with millions of votes cast as part of this year's competition.
Comedian Joel Dommett hosted the evening and described Rob as "inspirational" in an introduction.