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The man in his 40s developed a mild case of the illness several days after returning to Sydney from a trip to Europe.
He then went to his GP with symptoms that resembled monkeypox and after urgent testing health authorities believe it is a case.
Testing to confirm the virus is currently underway.
The man and a household contact are isolating at home.
Monkeypox is a rare viral infection that does not spread easily between people and is usually associated with travel to Central or West Africa.
Symptoms of monkeypox include fever, rash and swollen lymph nodes.
The World Health Organisation (WHO) said monkeypox symptoms are “very similar to those seen in the past in smallpox patients, although it is clinically less severe”.
It is transmitted to humans through close contact with an infected person or animal, the WHO said.
The WHO said vaccines used to eradicate smallpox also provide protection against monkeypox.
“Cases are occasionally reported in non-endemic countries in returning travellers or their close contacts, or in owners of imported pets,” NSW Chief Health Officer Kerry Chant has said.
“People can contract monkeypox through very close contact with people who are infected with the virus.”
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“The infection is usually a mild illness and most people recover within a few weeks.”
Health authorities are working to monitor for any more cases in Australia.
Cases have been identified in non-endemic countries like the US, UK, Spain and Portugal.
There are at least seven cases in Spain, 14 in Portugal, nine in the UK, and one case in the US.