Poundworld has collapsed into administration, putting more than 5,000 jobs at risk, following the failure of rescue talks over the weekend.
Joint administrator Clare Boardman said: "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".
Other parties named as possible buyers for the business, which is owned by TPG Capital, were turnaround specialist Alteri Investors and Poundworld's founder Chris Edwards, but a deal couldn't be struck.
Partners at Deloitte have been appointed joint administrators of the 335-strong chain.
Deloitte will try to find a buyer for the business, and has said there are no redundancies or store closures at this time.
Several retailers have shown significant financial distress this year, with both Maplin and Toys R Us disappearing from the high street.
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Restaurant groups including Carluccio's, Prezzo and Byron have also been shutting dozens of branches as they are squeezed by rising costs and a fall in consumer spending.
A TPG spokesperson said it was a "difficult decision for every party involved".
There remains optimism that a proportion of the chain's staff will avoid losing their jobs if buyers can be found for part of the business during the administration process.
"Despite investing resources to strengthen the business, the decline in United Kingdom retail and challenging behaviour affected Poundworld significantly".
Poundworld, which also trades under the name Bargain Buys, welcomes two million customers through its doors each week and competes with the likes of Poundland and Poundstretcher.
Others undertaking CVAs include New Look, Mothercare and Carpetrights.