Victorian senator Richard Di Natale has been elected unopposed in a ballot to replace Christine Milne as Greens leader.
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Queensland senator Larissa Waters and WA senator Scott Ludlam have been named "co-deputy leaders" - replacing Melbourne-based Greens MP Adam Bandt - after standing unopposed.
Party whip Rachel Siewert confirmed the new leadership after a ballot on Wednesday morning.
Senator Milne announced her resignation as leader on Wednesday morning, bringing to an end a 25-year political career.
Senator Milne said she had made the decision to resign after speaking with her family.
"It is with a mix of optimism, pride, excitement and sadness that I am resigning the leadership and leaving the Senate", she said.
The preselection process in Senator Milne's home state of Tasmania opens shortly.
Senator Milne was elected to the Senate in 2004, was elected deputy leader in 2008 and became leader in 2012 after the resignation of Bob Brown.
She entered politics 25 years ago when she was elected to the Tasmanian parliament and became the first woman to lead a political party in Tasmania in 1993.
Senator Milne said she had achieved what she set out to achieve since taking over the leadership of the federal party.
"The Greens have gone from strength to strength with solid election results and a growing, engaged party membership," she said.
"I promised a more cabinet-style, collaborative approach to leadership. I am so proud of the way my colleagues have responded. We are a strong, capable, visionary Greens team.
"We have stood strongly for a safe climate and an end to wealth inequality. We have stood with the community against the cruelty of the Abbott government, with their first budget resoundingly rejected by the people, and the Senate."
Christine Milne announced she will not contest the 2016 election and has stepped down as leader of the Greens. David Pope has selected some of his favourite cartoons of the Senator.
Surprised Tasmanian Greens will start a priority search for a candidate to succeed Senator Milne, despite her assurance she will stay in the chamber after resigning as leader.
"It's not a panic situation," said party state convenor Austra Maddox. "But it's very critical we get the best possible person in place as soon as we can."
Ms Maddox said Senator Milne had told her by phone on Wednesday she would remain in the Senate.
"I am calling an urgent meeting of the state executive tomorrow night to discuss this," she said.
