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Catalytic hydrodechlorination is an efficient technology for degrading organochlorinated compounds, such as chloroform (CF), into harmless products. Compound-specific stable isotope analysis (CSIA) of multiple elements is widely used for the investigation of degradation mechanisms. Yet, its application in the study of catalytic hydrodechlorination is still limited. We have applied CSIA to derive chlorine, carbon, and hydrogen isotope enrichment factors (ε) during the degradation of CF over Pd/Al₂O₃ and over Rh/Al₂O₃. In addition, the enrichment factors for the same isotopes were derived for the reaction of CF with zero-valent iron (ZVI) for comparison. For the reactions of CF over Pd/Al₂O₃ and Rh/Al₂O₃, εC values (−21.9±0.25 ‰ and −23.4±2.3 ‰) and εCl values (−12.1±1.7 ‰ and −10.3±0.6 ‰) were determined, respectively. The corresponding εC and εCl values, for the dechlorination of CF with ZVI were −22.2±2.8 ‰ and −4.7±0.45 ‰, respectively. The apparent kinetic isotope effects (AKIE) of Cl suggest that the transformation mechanism in the catalyzed hydrogen-water system is a non-concerted reaction, unlike the known reductive dechlorination of CF with ZVI. Moreover, dual-isotope slopes (ΛC/Cl) for both catalyzed reactions (ΛPd = 1.8±0.13 and ΛRh = 2.1±0.14) are markedly different than for the ZVI (ΛZVI = 5.8±0.41), reflecting that the reactions proceed in different mechanisms. For hydrogen isotopes, while there was no clear trend for the catalyzed reactions, an inverse secondary hydrogen isotope effect was observed for the reaction of CF with ZVI.