The Middlesex paceman has been named in the side to take on the Proteas in the third Test, with the four-match series currently tied at 1-1.
Roland-Jones replaces Mark Wood after the Durham bowler was ruled out with a heel injury.
"Wood is not 100% fit so he's going to miss out this week and Toby Roland-Jones comes in for a debut," captain Joe Root told reporters.
"Toby has been, in the lead-up to the other games, really good in practice and he has obviously had a fine couple of years and it is a very exciting time, as it is for anyone who makes their Test debut.
"I'm really excited for him and I'm sure he's desperate to show everyone what he can do with the red ball for England."
Roland-Jones's county teammate Steven Finn has also been called up on standby.