Officers at the police academy in Glen Waverley and Broadmeadows police station will leave their posts for 30-minute blocks on Thursday as part of a series of stop-work meetings.
Dozens more sites are expected to be added at a rate of two stations each day, as the union tries to drag the government and Victoria Police back to the bargaining table.
Police want a 24 per cent pay rise over the next four years and the introduction of 8.5-hour shifts.
In May, an in-principle agreement was reached with officers for a nine-day fortnight and a 16 per cent pay rise over four years, but police union members voted against the deal.
The long-running pay battle is now before the Fair Work Commission after the force asked it to intervene.
Victorian officers want a 24 per cent pay rise over four years and 8.5-hour shifts. (Tracey Nearmy/AAP PHOTOS)
Victorian Police Association secretary Wayne Gatt warned other states including NSW and Queensland were attracting prospective officers with more lucrative pay and conditions.
"What will we say when people migrate north to brighter and better paid careers in NSW and Queensland?" Mr Gatt told Nine's Today Show on Thursday.
NSW officers will become the best paid in the nation following a "generational" pay deal which lifts wages at least 25 per cent, while Queensland Police offers a $20,000 relocation payments for recruits.
"You've got to grapple with this. We've got soaring crime in Victoria, a state of law and disorder, not law and order, and our members are powerless to stop it because we're losing cops," Mr Gatt said.
The union boss has denied some officers are facing an internal backlash for working voluntary duties against the boycott.
"Some of our members need a pay rise so badly that they can't afford to participate in that (voluntary duties boycott)," he said on Wednesday.
"We understand that and we also understand that that can cause tension."
Police union boss Wayne Gatt has downplayed tension over officers working voluntary duties. (Con Chronis/AAP PHOTOS)
Opposition Leader John Pesutto reiterated his call for Premier Jacinta Allan to intervene to broker a deal and said he trusted police not to jeopardise community safety.
Police Minister Anthony Carbines backed the commission to find a resolution.
"Police deserve a pay rise," he said.
"We put offers to Victoria Police members via Victoria Police and the Police Association. They voted that deal down."
NSW Police on Monday won a pay increase of up to 40 per cent, making them the best-paid in the nation.
More than 10,000 constables, senior constables and sergeants will receive increases of at least 25 per cent before shift allowances while pay scales have been simplified.
