Rokocoko replaces benched Cory Jane but there is no place for Jimmy Cowan with Brendon Leonard in at scrum-half.
The Springboks have recalled JP Pietersen, Bryan Habana and Jean de Villiers for their first game.
They are three of six changes made to the starting XV that lost 28-9 to the British and Irish Lions this month.
Ruan Pienaar plays at fly-half in Bloemfontein instead of Morne Steyn, hero of the second Test against the Lions, who drops to the bench.
Pierre Spies and Bakkies Botha are also in the South Africa team with Steyn, Wynand Olivier and Ryan Kankowski named as replacements.
Tri-Nations Series
South Africa vs New Zealand
Match schedule
Date: Saturday, 25 July 2009
Kick-off: 16:00BST
Venue: Bloemfontein
Competition : Tri-Nations Series
Live / Repeat: Live
Odwa Ndungane, Jongi Nokwe, Johann Muller are left out.
"It was a difficult decision to choose between Ruan and Morne, you always have difficult decisions as a coach," said coach Peter de Villiers.
"In rugby, you can't look too far ahead, so I will say that if injury hits, we will consider starting Steyn at fly-half."
Centre Adrian Jacobs failed to recover from a torn groin muscle and is replaced by Jaque Fourie, who resumes his midfield partnership with Jean de Villiers.
"It was a big setback to lose Adi, as he has been in our plans for a long time," added De Villiers.
"But with Jaque coming in, our plans won't change that much. They are very similar players and we will look to play a similar style of rugby with Jaque now at number 13."
Schalk Burger is still serving his ban for eye-gouging, leaving Heinrich Brussow to continue as openside flanker.
South Africa are hoping to beat New Zealand in Bloemfontein for the first time, having lost 15-9 to the All Blacks in 1976 and drawing 11-11 in 1960.
New Zealand hooker Keven Mealamu, captain Richie McCaw, Conrad Smith and Isaac Ross all came through light training on Monday after sustaining injuries in Saturday's win over Australia.
McCaw, Smith and Ross make the starting XV with Mealamu, who is set to be the seventh-most capped player, named as a replacement.
Coach Graham Henry told the All Blacks website: "We were really happy with the effort and the progress made against Australia and we are looking for continued improvement in the first Test against South Africa.
"It will be a massive challenge against our old foes."
New Zealand beat Australia 22-16 in the opening Tri-Nations match last weekend.
South Africa: Steyn, Pietersen, Fourie, De Villiers, Habana, Pienaar, Du Preez; Pierre Spies, Smith, Brussow, Matfield, Botha, Smit (cpt), Du Plessis, Mtawarira.
Replacements: Ralepelle, Du Plessis, Rossouw, Kankowski, Januarie, Steyn, Olivier.
New Zealand: Muliaina, Rokocoko, Smith, Nonu, Sivivatu, Donald, Leonard, So'oialo, McCaw (cpt), Kaino, Ross, Thorn, Tialata, Hore, Woodcock
Replacements: Mealamu, Owen Franks, Eaton, Read, Weepu, McAlister, Jane
Replacements: Ralepelle, Du Plessis, Rossouw, Kankowski, Januarie, Steyn, Olivier.
New Zealand: Muliaina, Rokocoko, Smith, Nonu, Sivivatu, Donald, Leonard, So'oialo, McCaw (cpt), Kaino, Ross, Thorn, Tialata, Hore, Woodcock
Replacements: Mealamu, Owen Franks, Eaton, Read, Weepu, McAlister, Jane
