Separation of dichlorobenzene (DCB) isomers with high purity by time− and energy−saving methods from their mixtures is still a great challenge in the fine chemical industry. Herein, silicalite-1 zeolites/polydimethylsiloxane (PDMS) hybrid membranes (silicalite-1/PDMS) have been successfully fabricated on the porous polyvinylidene fluoride (PVDF) supports to first investigate the pervaporation separation properties of DCB isomers. The morphology and structure of the silicalite-1 zeolites and the silicalite-1/PDMS/PVDF hybrid membranes were characterized by XRD, FTIR, SEM and BET. The results showed that the active silicalite-1/PDMS layers were dense and continuous without any longitudinal cracks and other defects with the silicalite-1 zeolites content no more than 10%. When the silicalite-1 zeolites content exceeded 10%, the surfaces of the active silicalite-1/PDMS layers became rougher, and silicalite-1 zeolites aggregated to form pile pores. The pervaporation experiments both in single-isomer and binary−isomer systems for the separation of DCB isomers was further carried out at 60 °C. The results showed that the silicalite-1/PDMS/PVDF hybrid membranes with 10% silicalite-1 zeolites content had better DCB selective separation performance than the silicalite-1/α−Al₂O₃ membranes prepared by template method. The permeate fluxes of the DCB isomers increased in the order of m−DCB < o−DCB < p−DCB both in single-isomer and binary-isomers solutions for the silicalite-1/PDMS/PVDF hybrid membranes. The separation factor of the silicalite-1/PDMS/PVDF hybrid membranes for p/o−DCB was 2.9 and for p/m−DCB was 4.6 in binary system. The permeate fluxes of the silicalite-1/PDMS/PVDF hybrid membranes for p−DCB in p/o−DCB and p/m−DCB binary−isomers solutions were 126.2 g∙m⁻²∙h⁻¹ and 104.3 g∙m⁻²∙h⁻¹, respectively. The thickness−normalized pervaporation separation index in p/o−DCB binary−isomers solutions was 4.20 μm∙kg∙m⁻²∙h⁻¹ and in p/m−DCB binary−isomers solutions was 6.57 μm∙kg∙m⁻²∙h⁻¹. The results demonstrated that the silicalite-1/PDMS/PVDF hybrid membranes had great potential for pervaporation separation of DCB from their mixtures.