The STEP concept has successfully been demonstrated for driving chemical reaction by utilization of solar heat and electricity to minimize the fossil energy, meanwhile, maximize the rate of thermo- and electrochemical reactions in thermodynamics and kinetics. This pioneering investigation experimentally exhibit that the STEP concept is adapted and adopted efficiently for degradation of nitrobenzene. By employing the theoretical calculation and thermo-dependent cyclic voltammetry, the degradation potential of nitrobenzene was found to be decreased obviously, at the same time, with greatly lifting the current, while the temperature was increased. Compared with the conventional electrochemical methods, high efficiency and fast degradation rate were markedly displayed due to the co-action of thermo- and electrochemical effects and the switch of the indirect electrochemical oxidation to the direct one for oxidation of nitrobenzene. A clear conclusion on the mechanism of nitrobenzene degradation by the STEP can be schematically proposed and discussed by the combination of thermo- and electrochemistry based the analysis of the HPLC, UV–vis and degradation data. This theory and experiment provide a pilot for the treatment of nitrobenzene wastewater with high efficiency, clean operation and low carbon footprint, without any other input of energy and chemicals from solar energy.