Under the workplace reforms, employees will have the right to ignore unreasonable calls and emails outside of their rostered shifts.
The laws formally passed federal parliament after the House of Representatives on Monday signed off on changes brought forward by crossbench senators.
The right to disconnect was part of a broader package of measures, which also included greater rights for gig workers, as well as provisions for casual employees to transition into part time or full-time employment.
Workplace Minister Tony Burke said the measures were long overdue.
"Workers, as they've gone to having their own mobile phone over the last decades, have now waited too long just to know you don't have to constantly be on call," he told parliament.
"People have been waiting years for this moment, and it's time for people to get those rights and to get those rights today."
But opposition workplace spokesman Paul Fletcher decried the laws, saying the right to disconnect would be a profound change, and the measures were being rushed through.
"(The government) has recklessly introduced a change, the legislation, without any consideration, without any committee process, without any exercise, without consulting, to understand what the implications of it would be," he said.
The opposition have warned the right to disconnect would hinder businesses to respond during emergency situations, while promising to roll back the laws should they win the next election.
Employer groups have said this would end flexible working arrangements that allow workers to pick up their children or go to appointments.
Australian Council of Trade Unions Secretary Sally McManus said the claims were "typical scaremongering that we see every single time".
"It sounds internally contradictory to me," she told ABC radio on Monday.
At the next election, the Greens will fight for people's right to disconnect from Peter Dutton. — Adam Bandt (@AdamBandt) pic.twitter.com/RPl7FEVS9QFebruary 11, 2024
Greens leader Adam Bandt, whose party proposed the right to disconnect changes, said he had been overwhelmed by positive feedback.
"Too many people have been putting up with an interruption to their family lives and their home lives for far too long," he told parliament.
"This is a practical, commonsense right that will give people the right to switch off when they clock off."
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