Hoffman, who received an Oscar nomination yesterday for his performance in The Master, plays new gamemaker Plutarch Heavensbee.
The image, released by Entertainment Weekly, shows Hoffman alongside Woody Harrelson's Haymitch at a formal occasion in the Capitol.
The first image of Sam Claflin as Finnick Odair was released earlier this week, along with shots of Jennifer Lawrence, Josh Hutcherson and Liam Hemsworth reprising their roles as Katniss, Peeta and Gale.
The arena sequences in Catching Fire have been shot using IMAX cameras, and will be screened in IMAX format.
The Hunger Games: Catching Fire will be released on November 22.
Watch a clip from The Hunger Games below: