We report a simple approach for fabricating flexible, free-standing, catalytic films composed of graphene oxide/carbon nanotube–Au (GO/CNT–Au) composites by using a one-pot chemical reduction route. The catalyst film was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis and Raman spectroscopy to investigate the morphology, crystalline structure of the composites. The layered structure of the catalyst film is porous, flexible and exhibits excellent catalytic property in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) reaction. This study demonstrate here for simple yet effective synthesis of catalyst film with a number of advantages such as good strength, high stability, easy operation, and good reusability with minimal loss of activity.