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."
(c) Bank of England/PA Wire
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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