This will be the couple's first live performance after their marriage, which took place on Oct 16 in Mumbai, followed by a grand reception in Delhi last night.
The awards, which will be held on October 27, will also witness performances by dancing diva Madhuri Dixit, Parineeti Chopra and Priyanka Chopra.
"Barfi" star Priyanka unveiled the People's Choice Awards trophy yesterday and said she is looking forward to her performance at the show.
"I will be doing a stage performance and I love live stage. It's fun and a different kind of act. I am sure it will be very interesting," said the actress.
"Vicky Donor" actor Ayushmann Khurrana will be hosting the awards.
The People's Choice Awards will be a celebration of the various shades of entertainment, honouring exceptional talent across Bollywood, Music, Television and Sports.