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The owner of Poundland has agreed to take on the leases of dozens of Wilko shops.
Pepco Group, which owns Poundland in the UK, is expected to convert up to 71 Wilko stores to the Poundland brand.
Poundland boss Barry Williams said it recognised the last few weeks had been difficult for Wilko workers.
In a statement, the company said that Wilko staff would have priority when applying for new jobs at the Poundland shops.
Wilko fell into administration in August as it struggled with sharp losses and a cash shortage.
It was founded in 1930 and by the 1990s became one of Britain's fastest-growing retailers.
But the discount chain has faced strong competition from rivals including B&M, Poundland and Home Bargains, as the high cost of living has pushed shoppers to seek out bargains.
The first shop closures are taking place on Tuesday after administrators PwC failed to find a buyer for the bulk of the business.
Mr Williams, the managing director of Poundland, said in the coming weeks it would work quickly with landlords to get its new shops open.
It said that the announcement would mark some "positive news for customers and those high streets that faced the loss of an important retailer".
Rival B&M has also agreed to buy 51 of Wilko's buildings in a £13m deal, but it is understood the stores will not be run under the Wilko brand.