Compound-specific stable chlorine isotope analysis (CSIA-Cl) is an important method for identifying sources of organochlorine contaminants and helping assess their quantification of transformation processes. However, the present CSIA-Cl is challenged by either redundant conversion pretreatment or complicated mathematical correction. To overcome the mentioned problems, a novel method has been developed for the CSIA-Cl of eight organochlorine Pesticides using gas chromatography-negative chemical ionization mass spectrometry (GC-NCI-qMS) in this study. The instrument parameters, acquisition mode, and required injection amounts were optimized in terms of the precision of GC-NCI-qMS. An ionization energy of 90 eV and emission current of 90 A were selected, and the precisions for eight organochlorine Pesticides were in the range of 0.37‰-2.15‰ in single ion monitoring (SIM) mode when the injected amount was 0.50 mg L (. 0.5 ng on column). Furthermore, when standards from Supelco and O2si were calibrated using standards from AccuStandard regarded as external isotope standard, chlorine isotope composition of -hexachlorocyclohexane (-HCH) and 2, 2-dichloro-1, 1-bis (4-chlorophenyl) ethylene (, -DDE) in Supelco and O2si was confidently differentiated. The provenance identification method was validated by three organochlorine contaminated groundwater samples and showed a prospect in identifying the source of organochlorine Pesticides.