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.
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.
