The 28-year-old Essex player, batting at number three in place of the injured Gary Balance, will take confidence from his century for the England Lions in their recent warm-up game against the tourists.
But South Africa captain Faf du Plessis has warned him the game at The Oval will be a whole new experience.
"Well done to him for getting a 100 previously but I can promise you the intensity of a warm-up game versus a Test match is totally different," Du Plessis said on Wednesday.
"He will be playing against a different attack."
One of the biggest threats Westley faces will be 22-year-old paceman Kagiso Rabada, back in the South Africa team having missed their 340-run second test win at Trent Bridge through suspension, after swearing at England's Ben Stokes in the opening match at Lord's.
"I'm excited to see what KG is going to bring to this game," said Du Plessis. "With the time off, as a player it makes you a little bit hungry again, and the fact that we have done well in the previous game will add to his motivation.
"If the weather is like this, will be a bit bowling friendly so I assume he will be raring to get that ball in his hand."
The match at The Oval will be the venue's 100th test. The four game series is currently tied at 1-1.
(Reporting by Martyn Herman; edited by Julian Shea)
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