Gas separation membranes for natural gas are widely used. For efficient separation of CO2/CH4, high-performance gas separating polymeric blend membranes are desired. The main objective of this study is to synthesize blend membranes for removal of CO2 from CH4 using glassy and rubbery polymers with the addition of amine. The methodology comprises various contents of polyvinyl acetate (PVAc) ranging from 5 to 20 wt blended with polysulfone (PSU) and 10 wt MEA in DMAc solvent used for the formation of flat sheet membranes via solution casting method. The synthesized blend membranes possessed homogenous surfaces and showed a uniform packed bed of spherical structure, as seen from FESEM images. The existence of a single glass transition temperature for different blend membranes indicated miscibility among the polymeric blends, shown by DSC analysis. Thermogravimetric analysis showed an improvement in the maximum degradation temperature with the increase in PVAc content in the membrane blends. FTIR analysis confirmed the polymer blend�s miscibility with very few spectral peak shifts. The gas permeation results concerning MEA showed that CO2 permeance increased, in PSU and PSU 80/PVAc 20, from 39.63 to 63.97 at 2 bar pressure. EPBM is an appropriate tool for the production of novel materials with joined characteristics that improved application properties with low-cost advantage. © 2018 Bulgarian Academy of Sciences, Union of Chemists in Bulgaria