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 entire All Blacks apparel line has been updated for 2013/14. Check out the New Zealand All Blacks polo.
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The Gilbert Blitz 8S rugby cleat is a great cleat at a great price of $69.99. Get a new pair of cleats today.
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The NEW All Blacks 2013/14 jersey has arrived at World Rugby Shop. Dare to wear the colors of the All Blacks.