Details of the probe — which is being carried out by KPMG’s forensic team — are set out in a report sent to creditors last week.
Following the collapse of Unwins, former staff called for an investigation by the Department of Trade and Industry.
The business collapsed with debts of at least £30m, just nine months after it was bought by Devereux Montague, an investment vehicle backed by the Australian businessman Phillip Cook.
“We have commenced an early investigation into matters that have come to our attention . . . particularly the use of the bank accounts of DM (Devereux Montague) to bank Unwins’ takings in the period prior to administration,” states the 22-page report.
KPMG also reveals that it is investigating why the retailer “continued to trade whilst its stock holding had reduced to such a low level in late 2005”.
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“The investigations will enable us to consider whether there are any claims that can be made,” said the KPMG report.
However Cook strenuously denied any suggestions of wrongdoing.
He claimed that money had been transferred through Devereux Montague because of “extremely high levels of theft at Unwins”. He said: “I don’t care how it looks to an outsider — it was all audited and checked at the time. (KPMG) probably just want to earn some more fees.
“They can say that if they like, but there is not one shred of evidence,” he added.
KPMG declined to comment at this stage.
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Cook controlled his investment in Unwins through Devereux Montague Corporate Services and Interface Assets, both of which have failed to file accounts on time at Companies House.
“Our top two companies have not been able to file their accounts on time, or at all, because we have been working on unravelling the Unwins situation since March and this also affected the bottom companies, which in fact owned the off-licences,” said Cook.
The KPMG report also reveals that Revenue & Customs has lodged a claim for £16.1m in unpaid taxes.
Unwins’ unsecured creditors include InBev, the owner of Beck’s, which is owed £2.6m, and Diageo, which owns Smirnoff, which has £2m outstanding.
In total, unsecured creditors are thought to be owed at least £16m.
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The larger than expected claim from the Revenue makes it even more likely that unsecured creditors will not receive anything from the administration, despite the sale of large chunks of the business to Threshers, a rival off-licence chain.
According to the KPMG report, Threshers, owned by Terra Firma Capital Partners, the private-equity vehicle of City financier Guy Hands, paid £4.5m for the 200 stores.
Unwins, which employed 2,500 staff in almost 400 stores before its collapse last year, can trace its roots back to 1843. It had been owned since 1920 by the Wetz family, but had been hit hard by tough margins and increased competition from supermarkets.
Unwins is the latest in a string of retailers to have collapsed. Others include Courts, Allders and Kookai.