The gang used hi-tech equipment to turn out 24 bottles of vodka a minute at a warehouse in Hackney, East London.
HM Revenue & Customs said the evaded duty and VAT totalled £16 million.
They also produced 9.5 tonnes of counterfeit rolling tobacco with a duty value of £800,000.
Harvey Conroy, of Totteridge Park, north London, was jailed for 12 years and three men received sentences of 10 years: Steve Davis of Docklands, East London; Michael Oliver of Newport, Gwent; and Geoffrey Hall, of Newport Pagnall, Bucks.
Alan Saunderson, of Oakwood, north London, was jailed for eight years, and Christopher Hill, of Newport, Gwent, for six-and-a-half years.
All were charged with conspiracy to cheat the public revenue.
The gang ran a 24-hour operation at the warehouse using Polish workers brought to the UK solely for the purpose.
HMRC investigators worked with law enforcement agencies in the Netherlands, Germany, Belgium, Poland and Cyprus to bring the gang to justice.
The gang used ethanol from a vodka factory in Eastern Europe to make the fake vodka and the tobacco was stored in the Netherlands before coming to the UK.
It is thought that the packaging came from Cyprus.
Simon Grunwell, assistant director of HMRC criminal investigation, said: “HMRC is committed to protecting the public purse from attack by organised crime gangs trying to steal vast amounts of money.
“Where we find fraud we will act without delay to bring those responsible to justice.”