A modified hydrothermal method was developed to synthesize ZnO-CuO composite nanostructures. A free-standing film made of ZnO-CuO nanostructures was assembled on the surface of the hydrothermal solution with a smooth surface on one side and a spherical surface on the other side. The structure, growth mechanism and the optical properties of the composite nanostructures were studied. Structural characterizations indicate that the composite nanostructure mainly consisted of two single-crystal phases of CuO and ZnO. The sensitivity for CO gas detection was significantly improved for the composite CuO-ZnO nanostructure film. This method offers a possible route for the fabrication of free-standing nanostructure films of different functional composite oxides.