The singer revealed that she is "thrilled" to be performing on the show's opening day.
She said: "I am really looking forward to performing at Britain's Next Top Model Live. It sounds like an awesome day out and I'm thrilled to be headlining the first day!"
Suzy Pallett, event director, added: "We're delighted to be able to confirm Diana Vickers as our headline act for the launch of Britain's Next Top Model Live.
"We are really excited about this year's event and have a packed schedule of music, fashion, shopping, beauty and entertainment that we know our visitors are going to love.
"We hope that Diana's opening performance will be a fitting way to kick off this year's event in style."
Vickers will be performing on the Kiss Open Catwalk, an area dedicated to high fashion, music, Kiss DJ sets and entertainment features.
Britain's Next Top Model Live starts on October 22.