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The union representing workers at Wilko said the majority of stores are to close 'in a week' after a purchase fell through.
The decision means staff redundancies at the discount retailer will start in the coming week, the GMB union said.
It said that in a meeting with the company's administrator PwC, it was confirmed that there was no longer any prospect of saving the majority of the business.
The BBC has contacted PwC.
Wilko announced earlier this month that it was going into administration, putting 12,500 jobs and its 400 stores at risk.
PwC was appointed as the administrator, tasked with trying to find a buyer for the business.