Former rugby league star Williams starts at inside centre, while All Blacks coach Graham Henry has also named Israel Dagg in the full-back role, with Mils Muliaina not making the matchday 22 for New Zealand's World Cup opener.
Centre Conrad Smith and hooker Keven Mealamu join Muliaina in sitting out the Pool A encounter at Auckland's Eden Park.
Elsewhere, prop Tony Woodcock packs down alongside hooker Andrew Hore and tighthead Owen Franks in a side captained by flanker Richie McCaw, who wins his 99th cap.
Henry said: "There is real competition in a number of positions, at full-back and on the wings and other positions as well, and the selection of the starting XV reflects that.
"Those players selected have now been given the opportunity, which is exciting, and they will all look to make the most of their chance.
"Everyone in the All Blacks squad is excited by what lies ahead."
New Zealand team: I Dagg; R Kahui, M Nonu, S B Williams, I Toeava; D Carter, J Cowan; T Woodcock, A Hore, O Franks, B Thorn, A Williams, J Kaino, R McCaw (capt), V Vito.
Replacements: C Flynn, B Franks, A Boric, S Whitelock, P Weepu, C Slade, C Jane.
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