The drive toward greater application of membrane has resulted in its rapid development in natural gas processing industry. In this work, amine‐mediated membranes were tailored for CO2 removal from CO2/CH4 stream. The effects of various parameters such as amine concentration, microporous support, feed pressure and composition were examined to study the permeation behavior of pure and mixed gases. Generally, CO2 transport through the DEA‐PVA membranes was higher than that of MEA‐PVA membranes for approximately 70%. The membrane containing 15 wt% DEA and 35 wt% MEA revealed higher permselectivity. CO2 permeance enhancement of amine‐PVA membranes in comparison with neat PVA membrane, confirmed that CO2‐amine reaction was the dominant transport mechanism. Additionally, with increasing feed pressure, CO2/CH4 permselectivity decreased due to carrier saturation. However, lower partial pressure of CO2 was in favor of reaction mechanism in pure and mixed gas tests. On the other hand, CH4 is not significantly affected by feed pressure confirming that solution‐diffusion is the governing transport mechanism. Additionally, PTFE support with higher wettability showed better performance (+8%) regardless of amine type, concentration and feed pressure. DEA‐PVA membrane has exhibited good stability during 2 weeks, unlike MEA‐impregnated membrane, which was probably due to carrier degradation over time. POLYM. ENG. SCI., 54:1268–1279, 2014. © 2013 Society of Plastics Engineers