The 24-hour action on Monday means paramedics across the state will refuse "all staff movements" at stations as part of ongoing union efforts to improve emergency responder staffing and pay.
"Paramedics signing on tomorrow will refuse to travel from their designated station to help plug roster holes elsewhere," Australian Paramedics Association NSW president Chris Kastelan said in a statement on Sunday.
"We're taking action to demand a better resourced service. We want a fairer workplace for Paramedics, and improved coverage and care for our communities."
The union is pushing for an additional 1500 paramedics that it says are needed to turn around deteriorating ambulance response times across the state.
It also wants a pandemic payment, and a pay rise of more than 2.5 per cent.
In February, paramedics took a similar 24-hour action amid claims of worsening working conditions including staff doing 16 hour shifts without breaks.
NSW Ambulance said an Industrial Relations Commission meeting with the union was scheduled for Monday in a bid to "minimise disruption to health services".
"NSW Health meets regularly with unions to discuss paramedic awards and entitlements," a NSW Ambulance spokesperson told AAP.
"NSW Ambulance values and acknowledges the work of all paramedics and control centre staff who have worked so hard over the last two years of the COVID-19 paramedic."
Health Minister Brad Hazzard has been contacted for comment.
Monday's action is set to commence as day shift crews clock in from 6:15am.
It comes after thousands of nurses rallied outside NSW Parliament last month, as well as 25 locations around the state.
