Blonde Mollie was looking forward to the fund-rasing gig, tweeting before hand: "So excited for the @PoppyLegion launch tonight! Such an honour to be here."
Welsh TV personality Geffin Jones was on hosting duty at the launch, which also featured performances by Britain's Got Talent finalists Luminites, Tich, and The Poppy Girls, who gave a rendition of the official appeal single, The Call.
X Factor stars Union J were also thrilled to take part, as the appeal holds a special significance to several of the band members.
George Shelley explained after the show: "It was amazing to launch the Poppy Appeal this year.
"Personally, the poppy means a lot to us, it's a symbol of pride. I have a brother serving in the Royal Marines, Josh's dad was in the Navy for ten years, and Jaymi's uncle was in the RAF and fought in the Falklands War.
"We think of them, and all the others who have bravely served, every time we put a poppy on."