The solar thermal electrochemical process (STEP) has sustainably accounted for the solar thermo- and electrochemical oxidation of sodium dodecyl benzene sulfonate (SDBS) fully driven by solar energy, gaining a high efficiency with a fast rate by the combination of thermochemistry and electrochemistry. In this article, thermoinduced electrochemistry was resolved for an in-depth understanding of the STEP degradation of SDBS. We employed thermodependent cyclic voltammetry, temperature-dependent fluorescence-electrochemical spectroscopy, and time-dependent electrochemical current spectroscopy for studying the electrochemistry, including the reaction, pathway, and mechanism. First, thermodependent cyclic voltammetric spectra indicated that the SDBS in sodium chloride solution is oxidized via an indirect process initialized by active chlorine, substantially accelerating and completing the oxidation process. Second, temperature-dependent fluorescence-electrochemical spectra displayed the pathway and kinetics by finding the initial desulfonation and the subsequent breaking of the alkyl side chain and benzene ring. Finally, time-dependent electrochemical current spectra demonstrated that the initial desulfonation is the fast step by generating the high current and the subsequent breaking is the slow one by a low current response, which is in agreement with the temperature-dependent fluorescence electrochemical spectra. A panoramic view is proposed and schemed for fully understanding the process and mechanism of the STEP degradation of SDBS. Moreover, the efficiency and effectiveness of SDBS degradation were proven to be significantly enhanced by using the STEP in outdoor and indoor tests. It is a novel and energy-free route for wastewater treatment, accomplished by the synergistic use of solar energy without any other input of energy.