The main goal of this study was to examine the structural, optical and photoelectrochemical properties of WO3 and WO3/BiVO4 photoactive materials and to create electrodes suitable for use in photoelectrochemical processes. Therefore, WO3 photoelectrodes, WO3/BiVO4 photoelectrodes with two-layer structure and WO3/BiVO4 homogeneous mixture photoelectrodes were tested. The structure of the photoelectrodes was determined by the X-ray powder diffraction method, and the optical properties were examined by the ultraviolet/visible spectroscopy method. For electrochemical characterization, methods of linear voltammetry, electrochemical impedance spectroscopy, Mott-Schottky analysis were used, and the open circuit potential was monitored over time. The photoelectrochemical process of amoxicillin degradation was carried out using chronoamperometry. The influence of different electrolytes (NaCl and Na2SO4) and photoelectrode annealing on the success of amoxicillin degradation was observed. The efficiency of the process was determined by monitoring changes in amoxicillin concentration using high-performance liquid chromatography. The results of electrochemical characterization showed good photoactivity of WO3 and WO3/BiVO4 photoelectrodes. Monitoring the change of the open circuit potential and Mott-Schottky analysis showed that the analyzed photocatalytic materials were n-type semiconductors. The results of the HPLC analysis indicated that WO3/BiVO4 photoelectrodes with a two-layer structure are the most effective in the degradation of amoxicillin.