In this study, a new monitoring method was developed, titled infrared thermal imaging technology, which can effectively evaluate the thermal effect of the charge-discharge test in the vanadium/iodine redox flow battery (V/I RFB). The results show that the all-vanadium redox flow battery (all-V RFB) has a greater molar reaction Gibbs free energy change than that of the V/I RFB, representing a large thermal effect of the all-V RFB than the V/I RFB. The charge-discharge parameters, flow rate and current density, are important factors for inducing the thermal effect, because of the concentration polarization and the ohmic resistor. The new membrane (HS-SO3H) shows a high ion exchange capacity and a good ions crossover inhibitory for the V/I RFB system, and has a high coulomb efficiency that reaches 96%. The voltage efficiency was enhanced from 61% to 86% using the C-TiO2-Pd composite electrode as a cathode with the serpentine-type flow field for the V/I RFB. By adopting the high-resolution images of an infrared thermal imaging technology with the function of the temperature profile data, it is useful to evaluate the key components’ performance of the V/I RFB, and is a favorable candidate in the developing of the redox flow battery system.