In this study, novel mixed matrix membranes (MMMs) with hollow zeolite imidazole frameworks (H_ZIF-8) were introduced with regard to CO2/CH4 gas separation. H_ZIF-8 nanoparticles (low density and large BET surface area) and amphiphilic PVC-g-POEM (poly(vinyl chloride)-g-poly(oxyethylene methacrylate)) graft copolymer showed good interfacial properties and uniform distribution, which resulted in improved gas permeation properties interacted with PVC-g-POEM by secondary bonding interactions. Two Tg values expressed the glassy PVC chains and the rubbery POEM chains, suggesting that the copolymer had a well-defined and microphase-separated structure. We observed that H_ZIF-8 interrupted the mobility of polymer chain, contributing to the increased Tg, was dispersed homogeneously in the coopolymer matrix without noticable aggregation.