Modified ultra-porous ZIF-8 particles were used to prepare novel ZIF-8/Pebax 1657 mixed matrix membranes (MMMs) on PES support for separation of CO2 from CH4 using spin coating method. TEM and SEM were used to characterize modified ZIF-8 particles. SEM was also used to investigate the morphology of synthesized MMMs. The MMMs with thinner selective layer showed higher CO2 permeability and lower CO2/CH4 selectivity in permeation tests compared to MMMs with thicker selective layer. The plasticization was recognized as the main reason for rise in CO2 permeability and drop in CO2/CH4 selectivity of thinner MMMs. The gas sorption results showed that the high permeability of CO2 in MMMs is mainly due to the high solubility of this gas in MMMs, leading to high CO2/CH4 solubility selectivity for MMMs. The fractional free volume and void volume fraction of MMMs increased as the thickness of membrane decreased. Applying higher mixed feed pressures and permeation tests temperatures resulted in increase in CO2 permeability and decrease in CO2/CH4 selectivity. At highest testing temperature (60 °C), the CO2 permeability of synthesized MMMs with thinner selective layer remarkably increased.