Matfield, who has been troubled by a hamstring problem, takes over from John Smit as skipper.
Smit is rested to the bench, with Bismarck du Plessis handed a start instead of Smit at hooker.
"It is the first time since our first game that we have the privilege to select the team from 29 fit players," Springboks coach Peter de Villiers said.
"The one thing that stood out in the Samoa v Fiji game (last Sunday) was how good Samoa were at scrum time.
"They annihilated the Fiji scrums, so that is a bit of bother for us. But having Victor back in the lineout, that can be a great contest now. He understands the systems and he inspires people around him."
Team: P Lambie; J P Pietersen, J Fourie, F Steyn, B Habana; M Steyn, F du Preez; T Mtawarira, B du Plessis, J du Plessis, D Rossouw, V Matfield (capt), H Brussow, S Burger, P Spies.Replacements: J Smit, G Steenkamp, C J van der Linde, W Alberts, F Louw, F Hougaard, J de Villiers.
Gilbert has released a new line of rugby cleats. The Gilbert Virtuo 8S is part of the exciting new product. Check it out.
The Barbarians are one of the top invitational rugby sides with a long history and classic rugby jersey.
The Nike Tiempo is a solid rugby cleat and one of few styles still made from full-grain natural leather.
The Lions get ready for their matches with this green training jersey. It's what the players wear. Get in the Gear!
A cool looking all black rugby cleat with the high performance adidas is known for. Get in the Gear!
Wear the crest of the British and Irish Lions on your t-shirt. A great look for the summer.
$29.99
The Lions are ready to get their Australia tour underway. They arrive in Perth on Monday.
The New Zealand All Blacks training jersey for 2013/14. Get in the Gear!
The USA Rugby Pro Alternate rugby jersey is perfect for any fan of the Eagles. Get yours to wear during the summer Test matches.
The NEW All Blacks 2013/14 jersey has arrived at World Rugby Shop. Dare to wear the colors of the All Blacks.
