The electrodeposition of ZnO films was studied using potentiostatic mode in varying conditions including the presence of graphene oxide (GO) as a buffer layer and an additional deposition step. The obtained films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform Infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The effect of electrodeposition conditions on the adsorption and photocatalytic properties of ZnO nanostructured films was analyzed by using methylene blue (MB) as a model dye molecule and exposure to UV light. The results indicated a marked effect of GO content in the buffer layer and the duration of nucleation on the properties of electrodeposited ZnO films. Lower GO content and an additional deposition step of 60 s resulted in the best adsorption and photocatalytic activity, these being 7 and 5-folds, respectively, in comparison to ZnO in absence of these adjustments. The MB photodegradation was found to follow first-order kinetics, the rate constant reaching a value of 2.38 × 10