In the current work, thermal treatment, PDMS coating, and combined thermal treatment with PDMS coating methods were applied over NH2-MIL-53(Al)/cellulose acetate (CA) hollow fiber mixed matrix membranes (HFMMM) for CO2/CH4 and CO2/N2 separation. The results showed that upon thermal treatment at 170 °C, CO2/CH4 and CO2/N2 gas pair selectivities of HFMMM were improved from 9.1 to 9.9 and 7.7 to 8.4, respectively. On the other hand, CO2/CH4 and CO2/N2 gas pair selectivities of HFMMMs were improved from 9.1 to 14.1 and 7.7 to 12.0, respectively, after thermal treatment at 220 °C. Substantial increment in gas pair selectivities of the thermally treated fibers was mainly due to polymer densification, which condensed the voids between polymer and particles. Subsequently, PDMS-coated HFMMMs exhibited gas pair selectivities of 17.0 and 16.2, respectively, which were higher compared to the untreated and thermally treated HFMMM. Highest improvement of CO2/CH4 and CO2/N2 gas pair selectivities were found for combined...