More than 5,000 jobs are at risk after West Yorkshire-based Poundworld called in the administrators.
The budget retailer was in talks with private equity firm R Capital over the weekend, but is now calling in administrators at Deloitte after talks broke down.
"The retail trading environment in the United Kingdom remains extremely challenging and Poundworld has been seeking to address this through a restructure of its business", said joint administrator for Poundworld Clare Boardman.
The company, which is owned by TPG Capital, has 335 stores including more than 40 in Yorkshire and Lincolnshire.
Deloitte is likely to run another sale process once appointed as administrator. Losses reportedly jumped to £17.1million in 2016 to 2017, from £5.4m the year before.
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It is the latest blow for Britain's struggling high street, which has seen a string of retailers and restaurants shrink or collapse altogether in the face of rising costs and a squeeze on consumer spending.
It recently opened a large store in the centre of Bradford - bringing new life to Darley Street which has been hit by a wave of store closures.
In the meantime, they have said that no redundancies or store closes are planned during this period and Poundworld would continue to trade as usual while it sought a buyer.
'Unfortunately, this has not been possible.
A TPG spokesman said: "This was a hard decision for every party involved".
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Poundworld's collapse comes after electronics chain Maplin and Toys R Us - each with Stevenage sites - both went into administration this year.
"We invested in Poundworld because of our belief in how the company serves its customers and the strength of its employees".
The retailer's move comes just days after House of Fraser announced plans to shut 31 stores, affecting around 6,000 jobs.
Others undertaking CVAs include New Look, Mothercare and Carpetrights.
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