Chlorinated polyfluorocarboxylic acids (Cl-PFCAs) derived from the widely used chlorotrifluoroethylene (CTFE) polymers and oligomers may enter and influence the aquatic environment. Here, we report significant defluorination of Cl-PFCAs by an anaerobic microbial community via novel pathways triggered by anaerobic microbial dechlorination. Cl-PFCAs first underwent microbial reductive, hydrolytic, and eliminative dechlorination, and it was the hydrolytic dechlorination that led to significant spontaneous defluorination. Hydrolytic dechlorination was favored with increased Cl-substitutions. An isolated, highly enriched anaerobic defluorinating culture was dominated by two genomes closest to Desulfovibrio aminophilus and Sporomusa sphaeroides , both of which exhibited active defluorination of CTFE tetramer acid. It implies the critical role played by anaerobic non-respiratory hydrolytic dechlorination in the fate of chlorinated polyfluoro-chemicals in natural and engineered water environments. The greatly enhanced biodegradability by Cl-substitutions also sheds light on the design of cost-effective treatment biotechnologies, as well as alternative PFAS that are readily biodegradable and less toxic.