British Home Stores (BHS), founded in 1928, which employs 11,000 people is being described as the biggest high street failure in the UK for nearly a decade since the demise of Woolworths in 2008.
UK business secretary Sajid Javid said: "Worrying news for BHS workers this morning. Government is in close contact with the company's management at this difficult time".
In a statement, Duff & Phelps said: "The group has been undergoing restructuring and, as has been widely reported, the shareholders have been in negotiations to find a buyer for the business".
"These negotiations have been unsuccessful. In addition, property sales have not materialised as expected in both number and value. Consequently, as a result of a lower than expected cash balance, the group is very unlikely to meet all contractual payments," it said.
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"The group will continue to trade as usual whilst the administrators seek to sell it as a going concern. Further announcements will be made as appropriate in due course," the statement said.
The company, which has debts of more than 1.3 billion pounds, decided to bring in administrators after talks to sell some of its 164 UK stores to Sports Direct collapsed over the weekend.
Dominic Chappell, the owner of BHS, said in a letter to 11,000 employees on Sunday night: "It is with a deep heart that I have to report, despite a massive effort from the team, we have been unable to secure a funder or a trade sale".
He indicated in the letter that staff wages for this month would be paid by the administrators.
In March 2015, Retail Acquisitions, a consortium of financiers, bought BHS from the retail entrepreneur Sir Philip Green for 1 pound.
At the time, Retail Acquisitions had said they would deliver 160 million pounds of funding to help turn around the fortunes of the chain, but have not been able to raise the sum.