The use of potassium carbonate as a solvent for the absorption of carbon dioxide is constrained by slow absorption kinetics, which hinders the overall rate of mass transfer. In this work, the reaction rate is promoted by the electrostatic adsorption of carbonic anhydrase (CA) onto the surface of both a porous polypropylene (PP) and a non-porous polydimethoxysilane (PDMS) hollow fiber membrane via layer-by-layer (LbL) assembly. The rate of CO 2 absorption into K 2 CO 3 is increased approximately threefold when CA is adsorbed onto the PP membrane surface, while the absorption rate of the modified PDMS membrane was slightly lower, within 70 to 90% of the PP values. The results show that the ultrathin CA films are assembled mainly on the surface of the membranes and do not penetrate into the depth of the membrane pores. The CO 2 hydration is enhanced in all cases, and the wetting of the porous PP membranes is reduced significantly by the pore blockage induced by the LbL adsorption of the polyelectrolytes.