The campaign poses the question: Would You Have a Drink With You? and will run in cinemas and in the press.
The ads feature Stiles – best known for her role in the Bourne series of films – having a drink with a more glamorous but less friendly version of herself.
Andrey Skurikhin, partner at brand owner SPI Group, said: “The UK is a critical market for Stolichnaya, second only to the US in terms of volume.
“This campaign supports our plans to build awareness in this market.”