Auckland utility back Toeava has been capped three times by coach Graham Henry, and will play at centre at Eden Park - his first start on home soil.
Mils Muliaina moves to full-back, with Henry electing to put Leon Macdonald among his reserves.
Henry said: "'Ice' (Toeava) is a talented young man and the challenge of starting at centre against Australia is the next step in his development.
"We have a number of players in good form which gives us options.
"This move bolsters our options at 15, keeps Leon MacDonald fresh, and makes room for Isaia in the starting line-up."
Macdonald starts on the bench, with Toeava's provincial team-mate Doug Howlett returning on the right wing. Jason Eaton returns to partner Chris Jack at lock while Ali Williams moves to the replacement bench.
Luke McAlister has recovered from a jaw injury sustained playing for North Harbour and takes his place among the reserves.
Half-back Jimmy Cowan was not considered for selection due to an ankle injury.
Team: Mils Muliaina (Waikato), Doug Howlett, Isaia Toeava (both Auckland), Aaron Mauger (Canterbury), Joe Rokocoko, Dan Carter (Canterbury), Byron Kelleher (Waikato); Tony Woodcock (North Harbour), Keven Mealamu (Auckland), Carl Hayman (Otago), Chris Jack (Tasman), Jason Eaton (Taranaki), Jerry Collins (Wellington), Richie McCaw (Canterbury, captain), Rodney So'oialo (Wellington)
Reserves: Andrew Hore (Taranaki), Ali Williams (Auckland), Chris Masoe, Piri Weepu (both Wellington), Luke McAlister (North Harbour), Greg Somerville, Leon MacDonald (both Canterbury)