Highly porous polyether imide (PEI) hollow fiber membranes were fabricated through a phase-inversion process. Surface modification of the membranes was performed by coating an ultra-thin layer of 2-(perfluoroalkyl) ethanol (ZONYL). The properties of the prepared membranes were evaluated through field emission scanning electronic microscopy (FESEM), water contact angle, N2 permeation, overall porosity, critical water entry pressure (CEPw) and collapsing pressure experiments. From FESEM, the PEI membrane showed an open structure with large finger-likes cavities. By coating the ZONYL layer, the modified membrane presented improved outer surface water contact angle (105 °), CEPw (450 kPa), and collapsing pressure (750 kPa). The improved PEI-ZONYL membrane presented an almost stable CO2 absorption flux (6.8×10-4 mol/m2 s) during 72 h of the gas-liquid membrane contactor operation while a significant flux reduction was observed for the plain PEI membrane. Therefore, the improved membrane with high surface hydrophobicity and porosity can be a promising candidate for high performance gas-liquid membrane contactors.