Chris Evans, a Labor senator between 1993 and 2013, will start the role in December and shape reforms laid out in a recent review of modern slavery laws.
The commissioner will work with government to crack down on exploitative practices such as human trafficking, forced labour and forced marriages.
Other practices include deceptive recruiting and debt bondage.
After his time in parliament, Mr Evans worked as chief executive for the Global Freedom Network, an arm of human rights group Walk Free which works to tackle modern slavery.
Attorney-General Mark Dreyfus said Mr Evans led a merit-based selection process to win the role, which drew an $8 million commitment over four years in the 2023-24 budget.
"The Anti-Slavery Commissioner will further strengthen the work undertaken across government, business and civil society to prevent and respond to modern slavery by supporting victims and survivors, raising community awareness, and helping business address the risk of modern slavery practices in their operations and supply chains," he said.
A recent landmark report in NSW found an estimated 16,400 people were trapped in modern slavery.
The state's anti-slavery commissioner James Cockayne called for an urgent inquiry into the practice after identifying risks for temporary migrant workers in rural and regional NSW.
Agricultural workers on temporary migrant visas are often vulnerable to being exploited. (Dan Peled/AAP PHOTOS)
That study looked at modern slavery risks temporary migrant workers face in agriculture, horticulture and meat processing in more than 15 rural and regional NSW towns.
A review of Australia's Modern Slavery Act tabled in 2023 found "no hard evidence" the legislation was bringing meaningful change for people living in modern slavery conditions.
"There are occasional scattered instances of modern slavery incidents and victims being identified, but no strong storyline that the drivers of modern slavery are being turned around," the review read.
"Overall, it is said, there has been a major cultural change and a strengthening commitment to work and collaborate harder to combat modern slavery ... this is the early phase of a long journey."
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