Police allege the 32-year-old man on Wednesday ignited a water bottle containing an accelerant and threw it towards the station in Cockburn, south of Perth.
Officers were able to subdue the man and he was arrested at the scene. He was charged with endangering life and refused bail to face Fremantle Magistrates Court on Thursday.
A mental health assessment has been requested.
Police Commissioner Chris Dawson said it would be alleged the incident was partly motivated by the WA government's wide-reaching mandatory vaccination policy, which has also prompted death threats towards the premier.
"I know emotions are running high in the community but this is a very, very serious crime that this man has been charged with," he told reporters.
"People can be agitated about ideological views or whatever they're motivated by but you cannot go around lighting fires and threatening to throw Molotov cocktails.
"There have been threats made against the premier and other people, including police. We do not take this lightly - it is a serious crime to threaten to kill people."
Perth man Jamon Hartzer, 42, was last week charged over online threats to kill Premier Mark McGowan and other political leaders.
He was refused bail and will return to court next month.
Protesters also gathered over the weekend outside the premier's home, while his mobile number was bombarded with calls and texts after being leaked on social media.
The premier last week outlined mandatory vaccination requirements for most of the state's workforce, including a January 31 deadline which would coincide with the end of the school holidays and potential reopening of borders.
He has faced growing pressure to reveal when WA will abandon border closures as other states and territories cement their own plans.
Perth radio 6PR has reported WA will rejoin the rest of the nation on February 1, triggering an eight-week period of restrictions including venue capacity limits.
Mr McGowan has refused to narrow the timeline other than to say it would be after the summer school holidays and in the first half of the year.
"Those decisions haven't been made," he told reporters on Thursday.
WA's business community has urged the government to provide certainty amid ongoing labour shortages and declining confidence in the regions.
The premier has countered that argument by saying retailers and hospitality businesses are better off being able to operate without restrictions over Christmas.
He has promised to provide further clarity once WA's full vaccination rate exceeds 80 per cent.
WA's borders are open to travellers from Queensland, South Australia, Tasmania and the Northern Territory but the resumption of widespread domestic travel in coming months could prompt a return to isolation for the festive season.
Mr McGowan said he made no apologies for remaining cautious as Victoria on Thursday recorded 1923 new local infections and 25 deaths.
"The lesson out of Victoria today is we're not out of this yet," he said.
"We need to continue to be careful."
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