Application of membrane contactors in a combination of monoethanolamine as a solvent system for post-combustion CO2 capture has been extensively studied in the last decades. Due to the better performance to capture CO2 at low concentration, the potentialities of novel technology of supported ionic liquids membranes (SILMs) for absorption process in gas-liquid membrane contactor system are currently being explored to improve and compliment previous technology. In this study, a modified hydrophobic gas-liquid membrane contactor system was prepared using Liqui-Cel® parallel flow module as a membrane support and 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide [emim] [NTf2] ionic liquid as a supporting phase. Under moderate operating conditions, parallel flow mode and use of monoethanolamine (MEA) as an absorbent, the effects of absorbent temperature and gas velocity on the CO2 absorption efficiency and CO2/O2 selectivity were determined using this modified module. Further investigation to compare the performances of blank and modified membrane module was implemented at different temperatures (303–348 K) and gas velocities (4.63 × 10−6 to 3.70 × 10−5 m s−1). Results revealed that efficiency of the CO2 absorption process of the modified module is almost doubled with an average selectivity factor of CO2/O2 around 5 times compared to blank contactor system. Thus, this modified membrane contactor system had shown a great potential for further used in the real industrial CO2 capture and beneficial to bottleneck the issue of MEA oxidation that usually occurred in previous gas-liquid membrane contactor system.