The This Morning presenter, 38, took to the red carpet in a stunning black Christopher Kane midi dress, which featured a diamante neckline, with a pair of black heels.
But when she began posing for the cameras, Piers couldn't resist but jump into her shot and begin pouting.
One picture shows Piers pouting as Holly beamed at him.
But it seems she had enough after a few snaps and playfully shoved him out of the way.
Piers shared the pictures on Instagram alongside the caption: "Holly loved me wrecking her big red carpet moment.."
Holly also posted the snaps and wrote: "Caption competition... just going to leave this here with you.... buckle up @piersmorgan."
Piers later posed with his Good Morning Britain co-star Susanna Reid on the red carpet.
Susanna, 48, looked stunning in a red off-the-shoulder dress and silver glittery heels.
Meanwhile at the glitzy bash, new mum Stacey Solomon enjoyed her first red carpet event since the birth of baby Rex.
She wore a unique tiered Olivia Rubin metallic dress, platform metallic shoes and a pair of chandelier earrings.
The Loose Women star posed alongside boyfriend Joe Swash on the red carpet.
Other daytime TV stars also looked stunning at the awards, including Lorraine Kelly, Stacey's co-star Andrea McLean and Holly's telly pal Phillip Schofield.
ITV recently announced there will be huge schedule changes from January as Good Morning Britain and This Morning get extended by 30 minutes each day.
From January 6, Good Morning Britain will be extended by half an hour to run from 6am until 9am, Lorraine will move to 9am, followed at 10am by This Morning, also extended by 30 minutes, before Loose Women at 12.30pm, ending at 1.30pm.
Kevin Lygo, ITV Director of Television, said: "Live television is at the core of what ITV does and what we bring to viewers.
"Our new schedule presents the opportunity to engage with our audience throughout the first part of each day, with some of the most well-known shows on television, in a way that no other channel does."
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