When he takes to the pitch, the 37-year-old will beak the record of 2007 World Cup-winning skipper John Smit with his 112th appearance for the side as South Africa look to wrap up the two-test series with another thumping win.
Matfield will lead a side that has two changes from one that scored five tries in beating the Welsh 38-16 in Durban last weekend.
The first will be a new lock partner in Flip van der Merwe and the other at loose-head prop, where Tendai Mtawarira takes over from Gurthro Steenkamp.
"This is a fantastic accolade for Victor," Springbok coach Heyneke Meyer said in a SARU media release on Wednesday.
"He has been a terrific servant of the game in South Africa and has led his country with distinction since returning to the Green and Gold.
"When he returned to the game earlier this season, he set his goals on becoming a Springbok yet again and he's worked extremely hard to get there.
"I don't think anyone can doubt that he deserves his place in the team and he's also been a great interim captain, with Jean de Villiers out injured."
BOTHA RESTED
Van der Merwe, who was given last weekend off to attend his brother's wedding, will play alongside his Bulls team mate Matfield after Meyer opted to rest veteran Bakkies Botha, who was not even named on the bench.
"I've always preferred to stick with a winning combination and the changes to the team were both part of our planning," Meyer added.
"The backline really performed well last weekend and we would like to give them another opportunity to play together, as there were a number of new combinations.
"The same applies up front. Bakkies is fit for selection, but we decided to manage his workload this week and I know Flip, who has been outstanding in the last two seasons, will slot back in easily.
"The same goes for 'Beast' (Mtawarira), who upped the tempo with his work rate last weekend."
Centre Wynand Olivier, recalled to the squad this week after last appearing in the national team jersey in 2012, takes his place on the bench instead of injured flyhalf Johan Goosen.
Team:
South Africa: 15-Willie le Roux, 14-Cornal Hendricks, 13-JP Pietersen, 12-Jan Serfontein, 11-Bryan Habana, 10-Morné Steyn, 9-Fourie du Preez, 8-Duane Vermeulen, 7-Willem Alberts, 6-Francois Louw, 5-Victor Matfield (captain), 4-Flip van der Merwe, 3-Jannie du Plessis, 2-Bismarck du Plessis, 1-Tendai Mtawarira
Replacements: 16-Schalk Brits, 17-Gurthrö Steenkamp, 18-Coenie Oosthuizen, 19-Lood de Jager, 20-Schalk Burger, 21-Ruan Pienaar 22-Wynand Olivier, 23-Lwazi Mvovo
(Editing by John O'Brien)
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