The appointments of Patrick Harvie and Lorna Slater as ministers have been approved by MSPs.
At the Scottish Parliament, MSPs voted by 69 votes to 56 in favour of the Scottish Greens co-leaders becoming junior ministers.
Their new roles form part of the co-operation agreement reached between the SNP and the Scottish Greens, which was backed by party members at the weekend.
Harvie has been named as minister for Zero Carbon Buildings, Active Travel and Tenants’ Rights.
He will have responsibility over areas including active travel, heat networks, a new deal for tenants, building standards and energy efficiency.
Slater has been named as minister for Green Skills, Circular Economy and Biodiversity.
She will have responsibility over areas including the circular economy, national parks and natural heritage, nature recovery targets and a green industrial strategy.
Ahead of the vote on Tuesday, First Minister Nicola Sturgeon said that the deal reached between her party and the Scottish Greens represents a ‘new way’ of doing politics.
The SNP leader also insisted that the mandate for an independence referendum is “undeniable”.
Presiding Officer Alison Johnstone earlier confirmed that with Harvie and Slater’s move into government, the party will no longer be entitled to a leader’s question at First Minister’s Questions.
The Greens will also no longer automatically be called by Johnstone to speak at the start and close of debates.