The ten shilling note, to be auctioned later this month in Sydney, was uncovered in Scotland in a private collection.
The note was issued on the order of the NSW Governor Lieutenant-Colonel Lachlan Macquarie in 1817 by the Bank of New South Wales (now Westpac) on the day the bank opened, the 'Daily Telegraph' reported.
"We have put a conservative estimate of a quarter of a million dollars on it in the catalogue," said Jim Noble of Noble Numismatics.
"Even Westpac itself doesn't have one and all the experts believed none had survived," he said.
On April 8, 1817 the Bank of New South Wales opened for business with 100 ten shillings notes issued on the first day, the report said.
The first Commonwealth of Australia banknote worth 10 shillings printed in 1913 and numbered M000001 is also up for grabs at the auction.
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