Matfield will captain the Springboks at Newlands while Botha leads the World XV as the home side start their build-up to the World Cup in England and Wales that begins on Sept. 18.
After so much success together with the Bulls franchise and the Springboks, it is the first time in 17 years that the pair will be on opposite sides and Matfield said their friendship would be on hold.
"It was a very special combination and we've become great friends. Even our wives and kids have become great friends," he told reporters on Friday.
"I can't wait to walk out there on Saturday and do the coin toss with Bakkies. But while we are friends I know that won't change anything when we get on the field. I'm expecting things to be physical. Nobody will be holding anything back.
"Maybe Bakkies will just look at me when we get to a lineout and know what I'm thinking," added Matfield. "I've also played a lot of rugby with Flip (van der Merwe who will also play for the World XV) over the years. So it will be interesting."
Botha will be playing his final game after announcing his retirement from all forms of rugby in April and is equally eager to be re-acquainted with his old partner.
"I don't think many lock combinations have played so much together in history and now Victor and I are on opposite sides and we're going to shake hands when we're doing the toss and make more history," Botha said.
"It's a big honour for me and a privilege especially as it's my last game on South African soil."
Botha said his side wanted to test the hosts to help South Africa coach Heyneke Meyer's preparations for the Rugby Championship opener against Australia in Brisbane on July 18.
"We want to put a good game together and ask as many questions as possible to prepare the Springboks for next week and the World Cup," he explained.
(Reporting by Nick Said, editing by Tom Hayward; nick.said@thomsonreuters.com; Reuters Messaging: nick.said.thomsonreuters.com@reuters.net; +27 83 272 2948)
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