Banknotes featuring the King’s portrait are being issued from Wednesday for the first time.
The new banknotes will co-circulate alongside those featuring Queen Elizabeth II.
The portrait of Charles will appear on all four banknotes – the £5, £10, £20 and £50.
In line with guidance from the royal household, the new notes will only be printed to replace those that are worn, and to meet any overall increase in demand.
The approach aims to minimise the environmental and financial impact of the change.
Bank of England governor Andrew Bailey said: “We’re very pleased to be issuing the new King Charles banknotes.
“This is a historic moment, as it’s the first time we’ve changed the sovereign on our notes.
“We know that cash is important for many people, and we are committed to providing banknotes for as long as the public demand them.
“Bringing these new notes into circulation is a demonstration of that commitment.”
In April, the King was presented with the first banknotes bearing his portrait and described them as “very well designed”.
His mother, Queen Elizabeth II, was the first British sovereign to be given the honour of having her portrait on the notes, on the £1 in 1960.
People will be able to snap up the new-look currency at selected Post Office branches.
The Bank of England has put temporary facilities in place to allow people to obtain a limited amount of the King Charles III banknotes.
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It has set up a postal exchange service, running from 5-30 June, up to a limit of £300 per customer.
An application form and further details are on the Bank of England’s website.
Below is a list of the locations and postcodes for the Post Office branches where the notes will be available first on launch day:
Piccadilly Plaza (Manchester), M2 1BB
Sunderland City, SR1 1RR
Portsmouth, PO1 1AB
Birmingham, B2 4AA
The City of London, EC2M 5TE
Moorgate, EC2M 5TE
Broadway, SW1H 0AX
Great Massingham, PE31 6HP
Tetbury, GL8 8DB
Minchinhampton, GL6 9BN
Windsor, SL4 1AA
Houndsditch, E1 7BS
Woodstock, OX20 1SP
Poundbury, DT1 3AZ
Source Agencies