Under changes to the Law Enforcement Act that have the backing of the Islamic community, police can require anyone to remove a face covering - including a helmet, burqa, niqab or mask.
In most cases, the penalty would be a $220 fine, but cases involving motorists could incur penalties of up to a year in jail and a fine of $5500.
The NSW ombudsman will conduct a review of the new laws after 12 months.
"People will only be required to remove a face covering for as long as it takes to identify them," NSW Premier Barry O'Farrell said as he announced details of the new laws today.
"Those who want to be identified privately for cultural and religious reasons can request to go to a police station.
"I have every respect for different religions and beliefs but, when it comes to enforcing the law, the police should be given adequate powers to make a clear identification."
The changes, to be introduced into the NSW parliament next week, were drafted in response to the controversy surrounding a Sydney woman sentenced to jail for falsely accusing an officer of trying to remove her burqa.
The sentence against Carnita Matthews was later quashed after the District Court ruled there was no evidence to confirm it was she who filed the complaint, because the person wearing the veil could not be identified.
Police Association president Scott Weber said the new laws were overdue, and would help officers deal with "multicultural issues in a sensible way".
"We've seen time and time again that police officers have been hindered in regards to doing their jobs," Mr Weber said.
"A police officer should have the power to identify any motorist on a road in NSW to determine they're the driver of that vehicle, to make sure that all the community is safe, and the motorist has not committed any offence previously, and we can also give the ticket to the right person."
Mr Weber said the changes, flagged by Mr O'Farrell in July, had been embraced by the Islamic community.
"This is legislation that is commonsense, and I don't think anyone can negate it and say it's heavy-handed," he said.
"It's about making sure police officers can do their job and the community is safe."
The chairman of the Islamic Council of NSW, Khaled Sukkarieh, said the tough laws would have minimal impact on the Muslim community.
"We don't believe (the changes are) going to cause any problems for us," he said.
"This will be reviewed over the next 12 months as well, and ... if there are any issues that have been brought up, then obviously they'll be taken care of."
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