The blockade on a busy south Sydney road on Tuesday morning led NSW Premier Dominic Perrottet to call on his government to "throw the book" at the three women and one man from Fireproof Australia.
It comes after the NSW government passed legislation on Friday to clamp down on environmental activists who target roads and ports.
The laws mean demonstrators now face up to two years' prison and fines of $22,000.
The group, which blocked traffic on General Holmes Drive, allegedly failed to comply with police directions to move on and were arrested without incident, police said.
A 61-year-old ACT woman, a 48-year-old woman from East Lismore, a 31-year-old woman from Brighton Le Sands and a 46-year old Queensland man were charged with wilfully preventing free passage of a person or vehicle, refusing to comply with police directions, and refusing to disclose their identities when required.
They were refused bail and will appear in Sutherland Local Court on Tuesday.
The premier said he hoped his government's toughened legislation would act as a deterrent against disruptive activists.
"This type of behaviour needs to stop," he said.
While his government respected and promoted free speech, people must exercise their right to protest responsibly, he said.
"Don't do it at the expense of people trying to get to and from work, trying to get their kids to school, stopping people earning a living and a wage - that's what these protests are doing."
He warned activists they risked alienating the public and losing support for their cause.
That much was apparent on Tuesday morning shortly before four Fireproof Australia protesters were arrested.
"F***ing move, I've got to get to work," one man said, before attempting to drag one of the protesting women off the road.
His intervention came seconds after two other drivers had spoken to the group.
"I understand where you're coming from but can you just open up one lane so the people who need to get through can get through?" The driver of an SUV asked the blockading protesters in footage shared by Fireproof Australia.
"You're not making any friends by stopping people getting through, you're not getting any support," another said.
The group's "three basic demands" are to "immediately re-home flood and bushfire survivors", implement recommendations of the royal commission into the Black Summer bushfires including securing an Australian-based aerial firefighting fleet, and to "smoke-proof" schools, aged care and disability facilities.
Fireproof Australia spokeswoman Bonnie Cassen said the new laws were not protesters' primary cause of concern.
"We're more scared of what will happen when the climate crisis causes the breakdown of law and order than we are of fines and prison," Ms Cassen said.
Blockade Australia spokesman Greg Rolles told AAP on Monday the new laws were not dissuading blockading protesters.
The blockades were the product of decades of "every other kind of protest" not achieving results, Mr Rolles said.
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