Composite membranes typically used for gas separation are susceptible to interfacial voids and CO2 plasticization which adversely affects the gas permeation performance. This paper evaluates routes towards the enhancement of CO2 permeation performance and CO2 plasticization resistance of composite membranes using non-stoichiometric ZIF-62 MOF glass and cellulose acetate (CA). Single and mixed gas permeation results, obtained with CO2 and CH4, demonstrate that the presence of ZIF-62 glass in CA polymer enhanced the CO2 permeability and CO2/CH4 ideal selectivity from 15.8 to 84.8 Barrer and 12.2–35.3, respectively. The composite membrane loaded with 8 wt% of ZIF-62 glass showed the highest CO2 permeability and CO2/CH4 ideal selectivity of 84.8 Barrer and 35.3, which were 436.7% and 189.3% higher compared to the pristine CA membrane, respectively. A CO2 plasticization pressure of 26 bar was achieved for the composite membranes, which is 160% higher compared to the pristine CA membranes, at about 10 bar. The mechanisms for the materials stabilization and greater separation performance were attributed to higher pore size (7.3 Å) and significant CO2 adsorption on the unsaturated metal nodes followed by metal cites electrostatic interaction with CO2. These findings confirm the potential of ZIF-62 glass materials as promising materials solutions towards the design of composite membranes for CO2 separation at industrial scale.