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Central defender DeVere will effectively cover the departure of Phoenix skipper Andrew Durante, after he agreed to a one-season deal with the Kiwi club.
The 29-year-old DeVere will hope the move results in a change of fortune after he was dogged by knee problems, having made 45 appearances across the past five seasons in Brisbane.
He managed only five games last season.
It ends a second stint at the Roar, having begun his A-League career there from 2008-11 before four seasons with Korean club Gyeongnam FC.
DeVere's lone appearance for the Socceroos came in a 2-2 friendly draw with Germany in 2015.
"It's easy to continue playing in an environment you feel comfortable in," he said.
"But I feel that I always rise to a new challenge and I'm looking forward to beginning this journey in Wellington."
Phoenix coach Ufuk Talay described DeVere as among the most "accomplished" centre backs in the competition.
Durante, who has made an A-League-record 313 appearances, announced his Phoenix exit earlier this month and is believed to have signed with expansion club Western United FC.