A dual-anode consists of stainless steel and TiO 2 /Ti electrodes is used to study the kinetics of the degradation of hazardous chemicals exemplified by azo dye orange G (OG) using a coupling photoelectrochemical catalytic and photoelectro-Fenton (PEC/PEF) system. Concurrent generation of hydroxyl radicals on the TiO 2 /Ti photocatalyst and in-situ generation of Fenton reagents on the stainless steel electrode greatly enhances the performance of the PEC/PEF electrodes over that of the PEC and the PEF alone process. The efficiency of the PEC/PEF process is a function of Fe 2+ and H 2 O 2 concentration OH⋅ in the solution bulk, which promotes the oxidative degradation of OG and its byproducts. The mean carbon oxidation state (COS) is estimated to reflect the degree of mineralization. Based on the pseudo first-order kinetics with respect to OH[rad], OG, Fe 2+ , the corresponding reaction rates is established. UV–Vis spectrometry reveals the presence of four major intermediates, which helps establish the OG degradation pathways.