It is the first in 19 days of planned action in a long-running dispute with the 24-hour strike beginning at 4am today.
The planned industrial action include Black Friday week and Cyber Monday, as well as October 20 and 25, and November 28.
Royal Mail has warned letters will not be delivered and some parcels will be delayed.
This is the sixth strike by postal workers this year.
It follows the union’s ballot for strike action over pay, which saw members vote by 97.6 per cent on a 77 per cent turnout to take action.
The union is demanding that Royal Mail Group make an “adequate” pay award that covers the current cost of living increases for its members.
It said “in an economic climate where inflation looks set to soar to 18 per cent by January 2023, the imposition would lead to a dramatic reduction in workers’ living standards”.
CWU General Secretary Dave Ward said: “There can be no doubt that postal workers are completely united in their determination to secure the dignified, proper pay rise they deserve.
“When Royal Mail bosses are raking in £758 million in profit and shareholders pocketing in excess of £400 million, our members won’t accept pleads of poverty from the company.
“Postal workers won’t meekly accept their living standards being hammered like this any longer, and the leadership of Royal Mail must recognise this sooner rather than later.
“Our members deserve a pay rise that rewards their fantastic achievements in keeping the country connected during the pandemic, but also helps them keep up during this current economic crisis.
“We won’t be backing down until we get just that.”
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