The jobs of 12,500 staff across 400 high street shops are at risk.
The majority of Wilko stores are set to close within weeks after a purchase of the retailer fell through, a union has said.
In a meeting with administrators on Wednesday, the GMB union said it was informed there is no longer any prospect that the majority of the business will be saved.
It means redundancies for staff in stores and at call centres will begin within weeks.
The discount homeware and household goods chain employs around 12,500 staff across 400 shops.
Stores had been trading as normal and staff continued to be paid as administrators PwC were brought in.
Some stores may be bought, either individually or as part of larger packages of the business, but significant job losses are now expected.
A full purchase of the business had been said to be unlikely but there had been “hope”, GMB said, over “expressions of interest” in part of the business.
A deadline of Wednesday last week had been set to put forward offers for the company after its collapse into insolvency the week before.
The family-owned company was established by the Wilkinson family in 1930 and had been looking for new investment with the administrators for a number of months.
Like many other high-street outlets, Wilko was struggling with inflation and supply chain challenges in the wake of the pandemic.
An announcement from the administrators said: “Since our appointment as administrators of Wilko we have held extensive discussions with parties who expressed an interest in buying all or part of the business.
“While discussions continue with those interested in buying parts of the business, it’s clear that the nature of this interest is not focused on the whole group.
“Sadly, it is therefore likely that there will be redundancies and store closures in the future and it has today been necessary to update employee representatives.
“We know this will further add to the uncertainty felt by workers. We will be supporting staff through this deeply unsettling time, working closely with the government, JobCentre plus, unions and large employers to maximise possibilities for a rapid return to work for employees in the event of redundancies.
“In the immediate term, all stores remain open, continue to trade and staff continue to be paid.”
Andy Prendergast, GMB National Secretary, said: “GMB Union will continue to support members through this process and will fight to ensure members are consulted as per the law and that you receive every penny you are entitled to.
“We will fight to ensure Wilko bosses are held accountable for the simple reason our members deserve so much better.
“GMB will not forget the incompetence that has led to this collapse and will we not forget the dividends paid to the millionaires who gambled your jobs on their whims.”
The shadow business secretary, Labour’s Jonathan Reynolds, said the news was “devastating”.
The loss of Wilko shops “will have a massive impact on their high streets and my thoughts are with those Wilko staff and their families facing this dreadful news”, he said.
“Sadly, shuttered up shops and struggling high streets has become the norm after 13 years of Conservative economic failure.
“Labour has a plan for our high streets. We will tackle the things holding firms back by reforming business rates, cracking down on anti-social behaviour and putting an end to empty premises to bring shoppers back to their high street,” he added.
By Sarah Taaffe-Maguire, Business reporter
