Water condensation is a possible cause of membrane wetting in the operation of membrane contactors, especially under high-temperature conditions. In this study, water condensation in pores of polytetrafluoroethylene (PTFE) hollow fiber membranes was investigated during high-pressure CO2 absorption around 70 °C. It was found that the liquid accumulation rate in the treated gas knock-out drum was constant during continuous operation for 24 h when all experimental conditions were fixed, indicating a stable degree of membrane wetting. However, as the operating parameters were changed, the equilibrium vapor pressure of water within membrane pores could change, which may result in a condensation-conducive environment. Water condensation in membrane pores was detected and proven indirectly through the increase in liquid accumulation rate in the treated gas knock-out drum. The Hagen–Poiseuille equation was used to correlate the liquid accumulation rate with the degree of membrane wetting. The degree of membrane wetting increased significantly from 1.8 × 10−15 m3 to 3.9 × 10−15 m3 when the feed gas flow rate was reduced from 1.45 kg/h to 0.40 kg/h in this study due to water condensation in membrane pores. The results of this study provide insights into potential operational limitations of membrane contactor for CO2 absorption under high-temperature conditions.