The Wilko name will disappear from UK High Streets as a rescue deal for the chain fell through.
All of its 400 stores across the UK will close by early October, the GMB union has said.
It means redundancies now look likely for all 12,500 staff at the family-owned business.
It is understood no bidders are interested in running shops under the Wilko name, although some parties are interested in rebranding stores.
The billionaire owner of HMV, Doug Putman, hoped to keep up to 300 Wilko shops open, but his bid failed as rising costs complicated the deal.
Administrators are expected to announce the details of further redundancies and store closures soon.
The cash-strapped chain announced in August it had collapsed into administration, raising concerns over the futures of its 12,500 employees.
Administrators at PwC have already announced that some 1,016 redundancies would be made at 52 shops across the country that will close on Tuesday and Thursday this week.
Another 299 redundancies have taken place at its two distribution centres in Worksop and Newport, which will close on Friday next week, while more than 260 redundancies have been made at its support centre.
Proposals put forward by Canadian entrepreneur Doug Putman were hampered by the costs and difficulties thrown up by the need to overhaul Wilko’s supply chains.
He had originally been eyeing up to 300 shops, but the deal in its most recent form may have included about 100.
Day-to-day costs to keep everything running, rents and supplier contracts were also posing a challenge.
In a statement, Mr Putman said: “It is with great disappointment that we can no longer continue in the purchase process for Wilko having worked with administrators and suppliers over several weeks to seek a viable way to rescue it as a going concern.
“A stable foundation could not be secured to ensure long-term success for the business and its people in the way that we would have wanted,” he added.
After the collapse of Woolworths in 2008, Wilko – family-run until its problems came to a head – stepped up to fill the gap left on the High Street.
Founded in 1930 and well known for its affordable everyday items, it had been struggling with sharp losses and a cash shortage.
Nadine Houghton, national officer at the GMB union, said: “Wilko was far more than a brand, a retailer or the products it sold, it was the thousands of loyal team members now facing an uncertain future. “Wilko may have ceased genuinely being a family brand many years ago, but the staff kept the real family ethos of Wilko alive until the very end. It is the family that Wilko colleagues made for themselves that will be missed the most.”
The company has struggled with strong competition from rival chains like B&M, Poundland, The Range and Home Bargains, as the high cost of living has pushed shoppers to seek out bargains.
B&M has said it will take on up to 51 of Wilko’s 400 shops in a deal worth £13m.
Many Wilko shops are in High Street locations in traditional town centres. While these locations are convenient for shoppers without cars, since the pandemic there has been a shift to bigger retail parks and out-of-town options with more space, benefiting its rivals like B&M.
Poundland is also understood to be interested in buying up to 70 stores as a way of boosting its own portfolio.
The Wilko brand is also still up for grabs, with retailers including The Range proposing bids for the name specifically.
Wilko had already borrowed millions from restructuring specialist Hilco, cut jobs and rejigged its leadership team and sold off a distribution centre as it struggled with rising costs and keeping shops fully stocked.
Lisa Wilkinson, the retailer’s chairwoman until January this year and the granddaughter of the firm’s founder, recently said “everybody has thrown everything” at trying to save the business.