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The ministerial appointments include 20 inside Cabinet and four outside, along with the four previously announced roles for support parties.
Hekia Parata and Paula Bennett have both been promoted to the front bench. Ms Parata moves from No 20 to No 7, and picks up the education portfolio, while Ms Bennett moves from No 16 to No 9, and retains her social development and youth affairs portfolios.
Judith Collins, previously Minster for Police and Corrections, was also elevated, moving from No 7 to No 5. She picks up the justice, ACC and ethnic affairs portfolios.
Canterbury-based Amy Adams has been promoted to a minister inside Cabinet, and received the associate role for the Canterbury earthquake recovery, and the communications and information technology, and internal affairs portfolios.
Among the other notable changes, Steven Joyce made a significant jump from No 14 to No 4.
He gets a new portfolio called tertiary education, skills and employment. His portfolios also encompass economic development, science and innovation, and associate finance.
Anne Tolley, who was previously Education Minister, slips back from No 8 to No 13, and picks up responsibility for corrections and police.
Nick Smith also fell down the ranks, moving from No 6 to No 10, he retains the environment and climate change portfolios, and also picks up local government.
David Carter slips back one place to No 11, and his previous portfolios of agriculture, biosecurity and forestry have been combined to create a single portfolio of primary industries, which also encompasses fisheries and aquaculture.
Gerry Brownlee remains No 3, and resumes the role of Leader of the House, and Minister for Canterbury Earthquake Recovery. He also picks up the transport portfolio.
Deputy Prime Minister Bill English's finance portfolio now includes the infrastructure portfolio, and disarmament and arms control is incorporated into Murray McCully's foreign affairs portfolio.
Jonathan Coleman picks up defence, state services and associate finance, while Phil Heatley picks up energy and resources, and retains housing.
Other new ministers inside Cabinet include Nathan Guy and Craig Foss. Mr Guy picks up Immigration and Mr Foss gets broadcasting and commerce.
Jo Goodhew, Chris Tremain and Chester Borrows have been named as new ministers outside Cabinet, while Maurice Williamson was also reappointed to his customs, building and construction, land information and statistics portfolios, remaining outside Cabinet.
Mr Key said his new line-up combined fresh talent with experience.
"There has been a revamp of some portfolios, and some first-term Ministers have been rewarded for their performance.''
United Future leader Peter Dunne has been previously announced as Revenue Minister, while Act's John Banks received responsibility for regulatory reform and small business. In a deal signed yesterday, Maori Party co-leaders Pita Sharples and Tariana Turia both picked up ministerial roles, Dr Sharples Maori affairs, and Ms Turia Whanau Ora and disability issues.