In this study, a photocatalytic reactor with a novel engineering design has been used for the extended degradation of sulfamethazine (SMZ). The reactor employed four consecutive stainless-steel plates immobilized by tungsten-dope TiO₂ (W–TiO₂) using polysiloxane. The characterization of W–TiO₂ by X-ray diffraction (XRD), Raman spectroscopy, and energy-dispersive X-ray (EDX) denoted successful doping of tungsten in the lattice of anatase crystals of TiO₂ suggesting a high photocatalytic activity under UV and visible light. A Box-Behnken experimental design was employed for the optimization of the operating parameters such as solution pH, flow rate, and the initial SMZ concentration. The residual SMZ concentration was below the detection limit after 30 min of the photocatalytic reaction under the optimum operating conditions. A highly remarkable degradation of SMZ was observed in five consecutive cycles, which reveals an extended stable photocatalytic activity offered by the reactor design. The transformation products were identified by tandem mass spectrometry, and they were employed to propose the degradation pathway. These results highlight the importance of using the photocatalysts in retained forms and open additional avenues for the practical application of photocatalysis in wastewater treatment.