Three-dimensionally (3D) ordered macroporous ZnO film was fabricated on a glass slide by layer-by-layer depositing and hydrolysis of Zn(CH3COO)2using 3D-ordered latex film as template followed by calcination at 450 °C for 2 h to remove the organic template. The as-prepared 3D-ordered macroporous ZnO film was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), diffusive reflectance UV-visible absorption spectra (DRUV-VIS), photoluminescence (PL), and photoelectrochemical measurement. Its photocatalytic activity was evaluated by the photocatalytic degradation of crystal violet (CV) aqueous solution at ambient temperature under the irradiation of simulated solar light. It was found that the 3D-ordered ZnO film exhibits efficient photocatalytic activity for photodegradation of CV under the irradiation of simulated solar light.