Atomic H* has been regarded as the key active species for the electrocatalytic hydrodechlorination (ECH), and the electrode design and operation conditions are related to the atomic H* generation. However, there is limited understanding of how the operation parameters affect the atomic H* generation and utilization. Due to the fact that Pd was inefficient in water dissociation step, MnO2 was combined with Pd to construct a novel Pd/MnO2/Ni foam cathode. Cyclic voltammetry confirmed that Pd/MnO2/Ni foam cathode with MnO2 load of 0.51 mg cm(-2) possessed the highest atomic H* generation and ECH activity. Excessive Pd load (> 0.44 mg cm(-2)) was detrimental to ECH because of the side hydrogen evolution reaction (HER). Operation conditions (e.g. applied current and electrolyte concentration) would directly affect the cathode potential, which was an important indicator of the atomic H* generation. The optimal cathode potential was determined to be -0.85 V when the applied current was 10 mA in this study. The electrolyte concentration of 10-15 mM was able to provide sufficient atomic H* for ECH, while excessive input of electrolyte would favor HER but inhibit ECH. ECH at acidic and neutral/alkaline solution underwent different pathways for atomic H* generation and further affect the utilization of atomic H*. After 120 min reaction, > 70% of atomic H* could be selectively used for ECH at initial pH of 4.0 and 5.0, while only similar to 37% was used for ECH at initial pH of 7.0. This work correlated the reactivity of electrode with the atomic H* and cathode potential, which would provide strategies for ECH catalyst design and operation optimization.