Nanocage-like, hollow ZIF-8 (H-ZIF) polyhedral nanocrystals were synthesized via the use of seed crystals, epitaxial ZIF-8 growth, and excavation of ZIF-67 sacrificial templates. The highly porous and hollow structure of the H-ZIF polyhedral nanocrystals was confirmed by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction (XRD), and Brunauer-Emmett-Teller analysis. The H-ZIF nanocrystals were distributed in an amphiphilic poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer matrix to form mixed-matrix membranes (MMMs) for CO2/CH4 separation. The microphase-separated nature of the structure of the PVC-g-POEM was induced by the solubility difference between the hydrophobic PVC backbone and the hydrophilic POEM side chains. Specific interactions between the micro-structured PVC-g-POEM polymer matrix and the imidazole moiety of the H-ZIF enhanced the interfacial contact and improved the dispersion of the H-ZIF within the MMM; this was confirmed by XRD, FE-SEM, and differential scanning calorimetry. The hollow structure of the H-ZIF reduced the gas diffusion resistance of the MMM, resulting in increased gas permeability. Moreover, the molecular sieving properties and CO2-philic amine groups in the imidazole linkers of the H-ZIF led to high CO2 separation performance. The PVC-g-POEM/H-ZIF MMM exhibited an approximately fivefold increase in CO2 permeability, with a value of 210.6 barrer, compared to 43.5 barrer for a pristine PVC-g-POEM membrane with a CO2/CH4 selectivity of 14.3, which is close to upper bound reported by Robeson in 2008.