Predicting the fate of chloroethenes in groundwater is essential when evaluating remediation strategies. Such predictions are expected to be more accurate when incorporating isotopic parameters. Although secondary chlorine isotope effects have been observed during reductive dechlorination of chloroethenes, development of modelling frameworks and simulation has thus far been limited. We have developed a novel mathematical framework to simulate the C/Cl isotopic fractionation during reductive dechlorination of chloroethenes. This framework differs from the existing state of the art by incorporating secondary isotopic effects and considering both C and Cl isotopes simultaneously. A comprehensive general model (GM), which is expected to be the closest representation of reality thus far investigated, was implemented. A less computationally intensive simplified model (SM), with the potential for use in modelling of complex reactive transport scenarios, was subsequently validated based on its comparison to GM. The approach of GM considers all isotopocules (i.e. molecules differing in number and position of heavy and light isotopes) of each chloroethene as individual species, of which each is degraded at a different rate. Both models GM and SM simulated plausible C/Cl isotopic compositions of tetrachloroethene (PCE), trichloroethene (TCE) and cis-1,2-dichloroethene (cDCE) during sequential dechlorination when using experimentally relevant kinetic and isotopic parameters. The only major difference occurred in the case where different secondary isotopic effects occur at the different non-reacting positions when PCE is dechlorinated down to cDCE. This observed discrepancy stems from the unequal Cl isotope distribution in TCE that arises due to the occurrence of differential secondary Cl isotopic effects during transformation of PCE to TCE. Additionally, these models are shown to accurately reproduce experimental data obtained during reductive dechlorination by bacterial enrichments harbouring Sulfurospirillum spp. where secondary isotope effects are known to have occurred. These findings underscore a promising future for the development of reactive transport models that incorporate isotopic parameters.