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Accumulation of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated ethenes and ethanes due to its high toxicity. Since there can be several possible sources of VC and ethene at such sites, assessing the origin and fate of VC can be complicated. Aim of this study was to evaluate carbon isotope fractionation associated with various anaerobic processes that lead to the production of VC and ethene in view of using isotopes to evaluate the origin and fate of these compounds in groundwater. Microcosms were constructed using sediments and groundwater from a contaminated site and amended with potential precursors for VC and ethene production. In the microcosms with dichloroethene isomers, sequential reductive dechlorination was observed, and isotopic enrichment factors of −19.9 ± 1.5‰ for cis-1,2-dichloroethene, −30.3 ± 1.9‰ for trans-1,2-dichloroethene, and −7.3 ± 0.4‰ for 1,1 …