ZnO nanorods were grown on silicon (Si) substrates by two techniques: (i) Chemical Bath Deposition (CBD) and (ii) a CBD seed layer combined with Carbothermal Reduction Vapor Phase Transport (CTR-VPT). The structured ZnO nanorods were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and contact angle measurments. The photoelectrochemical property of ZnO nanorods were analyzed by linear voltammetry under UV-ABC light excitation. Using the ZnO nanorod samples as photoanodes, the removal of methylene blue (MB) as a representative organic compound was studied by the photoelectrocatalytic (PEC) technique applying a potential (E) of 0.6 V. For comparison purposes, experiments were performed under the same conditions using photocatalysis (PC), direct photolysis and using samples of pure Si (support material) as working electrodes in PEC. XRD analyses of ZnO prepared by both methods showed the expected ZnO wurtzite phase and a preferred c-axial orientation in the growth of the nanorods. The presence of ZnO was further confirmed by XPS and contact angle measurements showed that ZnO grown by CBD (ZnO/CBD) had a slightly hydrophobic behavior while ZnO grown by CTR-VPT (ZnO/CTR-VPT) is hydrophilic. Both ZnO sample types were shown to be photoactive, with ZnO/CBD showing higher resultant photocurrent compared to ZnO/CTR-VPT. For the degradation of MB 53% of the compound was removed using ZnO/CBD as a working electrode, while using the ZnO/CTR-VPT electrode led to a removal of 43% of MB. However, direct photolysis alone removed 39% of the MB. The lower removal of MB using ZnO/CTR-VPT samples was related to surface dissociation during the degradation process. The results show that ZnO nanorods prepared by the CBD techique are a promising photoelectrode for PEC applications. Our data also indicate that CTR-VPT-grown nanorods produce uniform nanorod arrays, but this uniform nanostructure deposit does not lead to any increase in PEC activity.