The attack took place early Monday morning in the small village of Midway, B.C., which is located on the U.S. border and about 468 kilometres east of Vancouver.
The detachment building and an RCMP truck sustained minor damage in the attack, said police.
"I've been in the RCMP for 15 years and I haven't seen a specific attack like this," said Cpl. Chris Tensen. "I don't know why. The Midway RCMP have never dealt with this male."
According to an RCMP media release, an officer inside the detachment heard something hit a window and saw a bright flash at about 12:10 a.m.
When he looked outside, the officer saw the male suspect pick up a flaming bottle and throw it at a police truck, which then caught on fire, said police.
Police said the Mountie left the detachment to confront the suspect who then jumped into a running vehicle and fled.
The attack lasted less than a minute, and Tensen said he doesn't believe the suspect realized an officer was inside the detachment at the time.
While the suspect was fleeing, the officer got the licence plate number of the vehicle and then put out the fire, said Tensen.
"There was minimal damage because I think the first attack spilled most of the accelerant on the ground because the bottle didn't explode," said Tensen. "The fire was put out right away."
The suspect was arrested about seven hours later, and is expected to appear in provincial court in Grand Forks this morning, he said.