The hybrid electrochemical system of photocatalytic fuel cell - peroxi-coagulation (PFC-PC) is a combined technology of advanced oxidation process (AOP) which involve the hydroxyl radical formation for simultaneous degradation of organic pollutant and electricity generation. The p-nitrosodimethylaniline (RNO) spin trapping technique was applied by analyzing the RNO bleaching performance to detect the OH[rad] at the PFC and PC reactors. The presence of UV light showed higher RNO bleaching rate at the PFC reactor (11.7%) with maximum power density (Pmax = 3.14 mW cm−2). Results revealed that the optimum of maximum power density was observed at iron plate size of 30 cm2. UV light became a limiting factor in the PFC system as a power source in the PFC-PC system. Meanwhile, iron plate plays an important role to supply the soluble Fe2+ ions by oxidation process and become a suitable catalyst for in-situ production of H2O2 and OH[rad] through the PC process to degrade the organic molecules.