The effect of rainfall on mass transfer across the air-water interface was investigated through the CO₂ absorption experiments in a turbulent open-channel flow with the free surface. The results show that the rainfall enhances both the turbulent mixing near the free surface on the liquid side and the CO₂ transfer across the interface. The mass transfer coefficient on the liquid side is well correlated by both the mean vertical momentum flux of rainfall, M, and the mean kinetic energy of rain droplets impinging on the unit area of the air-water interface, KEF. However, it was not concluded which of M and KEF is a better parameter for expressing the rainfall effects on the mass transfer. The comparison between the mass transfer coefficient obtained in this study and that obtained in wind-driven turbulence suggests that it is of great importance to consider the rainfall effect on the CO₂ exchange rate between the atmosphere and ocean in precisely estimating the global carbon cycle in a climate model.