Poly(ionic liquid)s (PIL) have emerged as a class of versatile polyelectrolites, that can be used to prepare new materials able to achieve superior performances compared to conventional polymers. The combination of PILs with ionic liquids (ILs) may serve as a suitable matrix for the preparation of membranes for gas separation. In this work, mixed matrix membranes (MMMs) combining a pyrrolidinium-based PIL, an IL and three highly CO2-selective metal organic frameworks (MOFs) were prepared. The different MOFs (MIL-53(Al), Cu-3(BTC)(2) and ZIF-8) were used as fillers, aiming to maximize the membranes performance towards the purification of syngas. The influence of different MOFs and loadings (0, 10, 20 and 30 wt%) on the thermal and mechanical stabilities of the membranes and their performance in terms of CO2 permeability and CO2/H-2 ideal selectivity was assessed. The compatibility between the materials was confirmed by SEM-EDS and FTIR spectroscopy. The prepared MMMs revealed to be thermally stable within the temperature range of the syngas stream, with a loss of mechanical stability upon the MOF incorporation. The increasing MOF content in the MMMs, resulted in an improvement of both CO2 permeability and CO2/H-2 ideal selectivity. Among the three MOFs studied, membranes based on ZIF-8 showed the highest permeabilities (up to 97.2 barrer), while membranes based on MIL-53(Al) showed the highest improvement in selectivity (up to 13.3). Remarkably, all permeation results surpass the upper bound limit for the CO2/H-2 separation, showing the membranes potential for the desired gas separation.