Javier Bardem's villain Raoul Silva is highlighted in the picture, which shows him in conversation with a handcuffed James Bond (Daniel Craig).
A recent TV spot also focused on the character of Silva, with Bérénice Marlohe's character Sévérine warning Bond that he has never experienced fear on this level before.
Director Sam Mendes has described Bardem's performance as "full of surprises".
> Daniel Craig contracted to star in 'at least' two more Bond films
> 'Skyfall' new video: Daniel Craig talks shooting in London
Skyfall will be released on October 26 in the UK and November 9 in the US.
Watch a trailer below: