The 85-year-old will chair the BBC One show for the first time on November 23, as the show celebrates 10 years of guest presenters.
Sir Roger said: "I'm really looking forward to appearing on one of my favourite shows and just hope Ian and Paul will treat this old English actor gently.
"If not, I'll press the button which releases their chairs into a piranha-filled pool below and will cackle wildly like Ernst Stavro Blofeld. Who said I wasn't a ham?"
Sir Roger starred in seven Bond movies and his appearance has been announced as the latest 007 movie Skyfall dominates the UK box office, following its world premiere last week.