Some local councils are to open to help push through last-minute applications to extend licences to provide alcohol, hot food or entertainment after 11pm.
Most of the businesses yet to apply are off licences and takeaways
Businesses have until midnight to apply for an automatic extension, but nearly 50,000 are likely to miss the deadline.
They will have to get a new application approved before 24 November, when the Licensing Act 2003 comes into force in England and Wales, or face closure.
A senior police officer has called for an early review of the law's impact.
Deputy Chief Constable of the British Transport Police Andy Trotter told BBC Radio 4's Today programme that police believe the extension of licensing hours could lead to "more binge-drinking and violence".
Mr Trotter said if police fears are borne out, the government should act to "turn off the tap" by again limiting access to alcohol.
Mr Trotter, who was until recently responsible for licensing in the Metropolitan Police, added that the new legislation would bring in "many useful powers".
Around 190,000 businesses are expected to apply for one of the government's new flexible licences.
Most of the 47,500 businesses - about 25% - yet to apply ahead of Saturday night's deadline are reportedly off-licences and takeaways.
Any late applications could face opposition from residents.
Virtually all pubs have applied, with most asking their local councils to extend their opening times by one or two hours.
A British Beer and Pub Association spokesman said only independently-owned free houses were likely to be at risk as major pub chains had made sure their permit applications were in place.
"However, real problems remain for other sectors, such as corner shops, restaurants and late-night food venues, which have not seen licence applications at the same high rates," he added.
"We appreciate the efforts councils are putting in to cope with a large number of applications, but in general it will not be a problem for pubs because we believe the vast majority already have their applications in.
"We have pulled out all the stops to complete the process on time.
"We have delivered our side, and are now looking to the local authorities to deliver.
"Over-zealous town hall bureaucracy and unnecessary hearings could well bring the process grinding to a halt."
Local Government Association chairman Sir Sandy Bruce-Lockhart said shifting the power to grant drinks, food and entertainment licences from magistrates to local authorities had "placed a real burden on businesses" and a strain on councils' resources.
"When November comes, you may find it difficult to order a round at your local, drop in for a bottle of wine at your corner shop or get a take-away after closing time."
A British Hospitality Association spokesman said: "Most sensible restaurants and hotels will have applied but there will be a lot of clubs and village halls that will not."