FedEx couriers have walked off the job with the industrial action expected to affect Christmas deliveries.
The Transport Workers Union says from Monday its members will participate in national rolling four-hour strikes this week.
The parties have been in dispute over pay and conditions for months with a string of strikes this year, as negotiations over a new enterprise agreement stalled again last week.
FedEx has told the union that workers who participate in four-hour stoppages will be locked out for the remainder of the shift and the following full shift, meaning many workers will lose two days' pay per action.
TWU National Secretary Michael Kaine says FedEx's decision provides workers with greater ability to take more disruptive industrial action.
"FedEx is cutting off its nose to spite its face," he said on Monday.
"Management would rather start an all-out brawl with workers at great cost to its business and customers than consider the reasonable solution brought to the table by union members," he said.
The TWU says rolling four-hour work stoppages starting will affect NSW and WA on Monday, and be rolled out on Tuesday in Victoria and Tasmania, and continue on Wednesday in Queensland and SA.
The union says further rolling actions will be determined by workers who are now able to walk off the job with minimal notice.
Australian Associated Press
