Officers were called to a 7-Eleven on Punt Road in Windsor about 12.30am, where they allege the woman assaulted an attendant before setting a fire inside the store.
9News understands the attendant was allegedly hit and threatened with a lighter by the woman.
Vision has emerged of police attempting to arrest the suspect.
The woman allegedly resisted the arrest, with officers deploying a Taser.
Police described the woman as being ”non complainant” upon arrival.
“On police arrival, officers observed a fire inside the store and challenged a woman who was allegedly armed with accelerant,” police said in a statement.
“The woman was non complainant and force was used including baton strikes and the deployment of a Taser.”
A man who witnessed the incident described the incident as scary.
“The police came within a minute and tried to stop this girl, because the fire at a service station is very dangerous,” he said.
“They came to stop this girl.”
The fire was extinguished and the service station suffered minor damage.
A 46-year-old Windsor woman was arrested and charged with criminal damage by fire, theft, resisting police and unlawful assault.
She has been bailed to appear at Melbourne Magistrates Court on May 2.