NSW candidate Lee Rhiannon has secured the Greens a Senate spot, robbing Labor of a third seat.
Following the distribution of preferences on Wednesday, the Australian Electoral Commission (AEC) confirmed Ms Rhiannon was one of six senators elected for NSW.
The result has ended the Senate career of Labor backbencher Steve Hutchins, who had been demoted on the ALP ticket to make way for former party general secretary Matt Thistlethwaite.
Mr Thistlethwaite and former defence minister Senator John Faulkner were both safe at one and two on the ALP's ticket, taking two seats for Labor.
The AEC also confirmed the Liberal Party had taken two seats, and the Nationals one.
The other successful candidates were Concetta Fierravanti-Wells and Bill Heffernan for the Liberals, and Fiona Nash for the Nationals.
Labor had been confident of picking up three Senate spots in NSW, but Ms Rhiannon, a former state upper house MP, delivered a solid campaign, crisscrossing the state to drum up the 600,000 votes she needed.
Her mammoth effort to get across the line paid off, while NSW dark horse Cheryl Kernot missed out on a spot.
The first and last Greens senator to be elected in NSW was Kerry Nettle in 2001.
She lost the seat at the 2007 election, when the party received just 8.4 per cent of the primary vote.
The winners will be formally declared elected at 11am (AEST) on Thursday.
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