In this study, we developed a novel cerium/ascorbic acid/iodine active species to design a redox flow battery (RFB), in which the cerium nitrate hexahydrate [Ce(NO3)3·6H2O] was used as a positive Ce3+/Ce4+ ion pair, and the potassium iodate (KIO3) containing ascorbic acid was used as a negative I2/I− ion pair. In order to improve the electrochemical activity and to avoid cross-contamination of the redox pair ions, the electroless plating and sol–gel method were applied to modify the carbon paper electrode and the Nafion 117 membrane. The electrocatalytic and electrochemical properties of the composite electrode using methanesulfonic acid as a supporting electrolyte were assessed using the cyclic voltammetry (CV) test. The results showed that the Ce (III)/Ce (IV) active species presented a symmetric oxidation/reduction current ratio (1.09) on the C–TiO2–PdO composite electrode. Adding a constant amount of ascorbic acid to the iodine solution led to a good reversible oxidation/reduction reaction. Therefore, a novel Ce/ascorbic acid/I RFB was developed with C–TiO2–PdO composite electrodes and modified Nafion 117–SiO2–SO3H membrane using the staggered-type flow channel, of which the energy efficiency (EE%) can reach about 72%. The Ce/ascorbic acid/I active species can greatly reduce the electrolyte cost compared to the all-vanadium redox flow battery system, and it therefore has greater development potential.