In this research, an orthogonal experiment (45) was conducted to explore the degradation of CT in Ti/Pd sealed cathode chamber, and electrochemical characteristics of electrodes were analyzed simultaneously, demonstrating its superior capability for the dechlorination of aqueous CT. The results showed there existed a suitable electrolytic condition for CT hydrodechlorination, when Na2SO4 concentration was 0.4 mg·L−1, current density was 12 mA·cm−2 and initial pH was 7 within 45 min electrolysis time, the 89.42 % of CT was degraded, and the complete vanishment of CT until 65 min occurred. SEM and EDS analysis were used to comprehensively characterize the Ti/Pd cathode. Besides, theoretical calculations showed that Pd modified cathode possesses excellent intrinsic catalytic activity. CV curves and K-L calculation elucidated the one-electron-transfer process underlying the stepwise dechlorination of chlorinated alkanes at the Ti/Pd electrode. Cl− index calculations verified that CT degradation was partial dechlorination. The scavenging activity test of atomic hydrogen (H⁎ads) proved the pivotal roles of H⁎ads in CT hydrodechlorination. The voltage control degradation pathway of CT was put forward, which aligned well with the kinetic model. Overall, the Ti/Pd cathode represents a promising electrode material with significant potential for CT degradation from aqueous solutions.