Herein the synthesis of ZnO nanorods (NRs) by means of the one‐ and two‐step electrochemical deposition (ECD) process is focused upon. A comparison of the crystal structure, morphology, optical properties, and photoelectrocatalytic (PEC) activities of nanostructured ZnO cultivated by the two methods is conducted. X‐ray diffraction (XRD) analysis reveals that all samples annealed at 300 °C are polycrystalline and have a hexagonal (wurtzite) structure and significant improvement in the crystallinity of the sample deposited by the two‐step process. The morphological characterizations show that the NRs are well hexagonal and well oriented in the same sample. The optical spectra show a transmittance higher than 70% and direct bandgaps of 3.12 and 3.04 eV for the samples synthesized by one‐step and two‐step electrodeposition, respectively. The PEC properties of the films obtained are studied and reveal an efficient and rapid rhodamine B (RhB) azo dye degradation. In addition, the scavengers of reactive species as well as the kinetics during degradation are also studied and show that the superoxide radicals contribute significantly in degradation.