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 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=3.14mWcm-2). Results revealed that the optimum of maximum power density was observed at iron plate size of 30cm2. 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 through the PC process to degrade the organic molecules.