Canberra outlined plans to block citizens travelling to terror hotspots in October amid concern about the flow of foreign fighters joining militant groups in the Middle East such as Islamic State, with 70 citizens believed to have already made the journey.
Under new laws, anyone who heads to nominated areas will face up to 10 years in jail.
"Under the provisions of our foreign fighters legislation, I have today declared al-Raqqa province an area where a listed terrorist organisation is engaging in hostile activity," Foreign Minister Julie Bishop told parliament.
"This now makes it an offence under Australian law to enter or remain in the province of al-Raqqa without a legitimate reason. Anyone who enters or remains faces a penalty of up to 10 years' imprisonment."
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Bishop said she had so far cancelled 75 passports and refused to issue 10 passports to prevent people travelling to conflict zones.
Prime Minister Tony Abbott previously said an estimated 100 Australians were also supporting jihadists within Australia with recruitment and funding, while 20 people who fought with terrorist groups in the Middle East had returned.
Canberra in September raised its terror threat level and carried out extensive raids in Sydney and Brisbane. In addition, Australia's intelligence agencies have been given enhanced powers.
There has been growing disquiet from governments around the world about the threat posed by thousands of foreign fighters who have joined IS and who could launch attacks in the West.
The United States' Secretary of State John Kerry Wednesday hosted the first high-level meeting of the 60-member coalition trying to crush IS in Iraq and in Syria in Brussels, with measures to tackle the flow of foreign fighters to the region on the agenda.