From January 1, staff will be able to access 20 days of paid leave per calendar year while those providing support to a family or household member who is a victim-survivor of domestic violence will be allowed to dip into their carer's leave balance.
The changes follow consultation with unions, government employers and family and domestic violence experts.
"As the largest employer in NSW, it is our government's responsibility to provide workers with the support and security to take time away from work to take the necessary steps to find safety for themselves and their family," Women's Safety Minister Natalie Ward said in a statement on Friday.
"Everyone has the right to be safe both at home and in the workplace, which is why we have made addressing the issue of women's safety and the prevention of domestic and family violence a priority with record funding to increase support across the sector."
Unions claimed credit for the announcement, saying the provision was worked out during the long-running Sydney Trains industrial negotiations but faced resistance from some cabinet ministers.
"When you give people the right to paid family violence leave, you give them more than an entitlement - you shift the culture," Unions NSW gender equity officer Karen Willis said in a statement.
"That is why we have campaigned so hard for this new entitlement, both at Sydney Trains and across the NSW public sector."
The changes come ahead of the federal government's proposal to allow any Australian worker, including casuals, to access 10 days of paid family and domestic violence leave by August 2023.
If passed, the federal legislation would increase the number of Australian employees with access to paid family and domestic violence from 1.3 million to 11 million.
All Australian workers are currently entitled to five days of unpaid family and domestic violence leave each year under the National Employment Standards.
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