Salman, who will be part of the show for the second time, will be accompanied by his brothers Sohail Khan and Arbaaz Khan.
Salman on Thursday night shared a photograph of himself along with his brothers and Karan from the set.
"At 'Koffee With Karan' shoot...Koffee century," Salman captioned the image.
At Koffee with Karan shoot #koffeecentury pic.twitter.com/E8R8yKYfFU
— Salman Khan (@BeingSalmanKhan) December 1, 2016
Karan thanked the "Dabangg" star for coming for the milestone episode.
"Thank you so much Salman for coming on our 100th episode of 'Koffee With Karan'...Koffee century," Karan tweeted.
The fifth season of the talk show, which airs on Star World, has seen a string of A-listers like Shah Rukh Khan, Alia Bhatt, Akshay Kumar, Twinkle Khanna, Ranveer Singh, Arjun Kapoor, Ranbir Kapoor and Varun Dhawan.
In the previous seasons of "Koffee With Karan", the show has hosted guests like Amitabh Bachchan, Kareena Kapoor Khan, Saif Ali Khan, Kajol, Rani Mukerji, Sanjay Leela Bhansali and Aishwarya Rai Bachchan.