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Charles cracked a joke as he arrived on the red carpet outside the Theatre Royal Drury Lane in London’s West End on Tuesday.
On the steps of the venue, he was greeted by impresario Lord Lloyd Webber, its owner, and the Lord Lieutenant of Greater London, Sir Kenneth Olisa.
Ahead of the ceremony, the prince spoke to Jonathan Bailey and Phoebe Dynevor, who star in Regency-era Netflix drama Bridgerton.
Bailey joked that he expected the hit show to “be on for the next 50 years” and told the prince the series has been shooting in Bath, before describing the city as “stunning”.
Ant McPartlin and Declan Donnelly hosted the annual awards for a 10th year and it will air on Thursday on ITV for the first time.
Before the show, the presenting duo told Charles they were looking forward to some “classic HRH bantz” and jokingly noted that he looked very disappointed each year when they returned as hosts.
As the prince met the celebrity ambassadors, a rumble of thunder was heard through an open window, prompting laughter from Charles, Good Morning Britain presenter Kate Garraway and actress Felicity Kendal.
Among the winners were a mother who overcame her experience of domestic violence to secure a job in the ambulance service and a young woman who was helped through her addiction issues by the Prince’s Trust.
Former Big Brother presenter Emma Willis and Melanie C of the Spice Girls took to the stage to present an award wearing matching pant suits in pink and purple respectively.
BBC host Clara Amfo jokingly congratulated her co-presenter Anne-Marie on making it down the on-stage stairs safely in a nod to her infamous fall at the Brit Awards.
The pop singer, 31, took a tumble while descending some steps during the annual ceremony at London’s O2 Arena in early February – but carried on to finish her performance.
Taking to the stage after the final award, Charles quipped, “Welcome to the Ant and Dec Prince’s Trust Tuesday Afternoon Takeaway”.
He addressed the impact of the pandemic on young people and stressed the importance of the trust’s work.
Actor Sir Ben Kingsley, Amal Clooney and adventurer Bear Grylls were also among the celebrity attendees.
Founded by Charles in 1976, the trust supports 11 to 30-year-olds across the UK who are unemployed, struggling at school or at risk of exclusion.
Theatre Royal Drury Lane has undergone major renovations in recent years, reopening in July 2021 with the Frozen musical currently showing.