The gas-liquid two-phase mass transfer process in microchannels is complicated due to the special dynamical characteristics. In this work, a novel method was explored to measure the liquid side volumetric mass transfer coefficient kLa. Pressure transducers were utilized to measure the pressure variation of upward gas-liquid two-phase flow in three vertical rectangular microchannels and the liquid side volumetric mass transfer coefficient kLa was calculated through the Pressure-Volume-Temperature correlation of the gas phase. Carbon dioxide-water, carbon dioxide-ethanol and carbon dioxide-n-propanol were used as working fluids, respectively. The dimensions of the microchannels were 40 µm×240 µm (depth×width), 100 µm×800 µm and 100 µm×2000 µm, respectively. Results showed that the channel diameter and the capillary number influence kLa remarkably and that the maximum value of kLa occurs in the annular flow regime. A new correlation of kLa was proposed based on the Sherwood number, Schmidt number and the capillary number. The predicted values of kLa agreed well with the experimental data.