Global warming is considered as a consequence of extensive use of fossil fuels. Post combustion CO2 capture is an interesting and alternative solution where mixed matrix membranes (MMMs) can be an exciting candidate. This research focuses on the optimization of MMM composition consisting of Pebax® 3533 as the polymer matrix and porous coordination polymer (PCP) MIL-178(Fe) as a filler for gas separation application. MIL-178(Fe) characterized with SEM, TEM and TGA were applied to compare bare polymer and MMM. Optimum composition of the MMM obtained was 5 wt.% MIL-178(Fe) in Pebax® 3533. Average thickness of the optimized dense MMM was 116 ± 8 µm. Such MMM showed CO2 permeability and CO2/N2 selectivity of 312 ± 5 Barrer and 25.0 ± 0.5, respectively, 12% and 25% improved regarding the bare membrane. Additionally, optimum MMM was applied for CO2/CH4 separation and successfully compared in terms of improved CO2 permeability and CO2/CH4 selectivity.