Display omitted •CO2 capture realized by chemical absorption in microchannel using MEA solvent.•Spiral baffle structure embedded in the microchannel to enhance the mass transfer.•Better CO2 absorption achieved at low Re numbers with small pressure drop increase.•New correlations proposed considering both structure and chemical reaction factors. This paper presents an experimental study on CO2 chemical absorption by Monoethanolamine (MEA) solution in microchannel. In particular, a novel spirally distributed baffle structure is proposed to be embedded into the microchannel so as to generate the swirling flow pattern and to enhance the mass transfer. The effect of spiral baffle structure on the two phase flow pattern transition, the CO2 gas void fraction, the pressure drop, and the mass transfer performance are characterized and discussed, under varied gas and liquid flow rates, and MEA concentrations. Results demonstrate that the spiral baffle structure could significantly enhance the gas–liquid mass transfer, with overall liquid side volumetric mass transfer rate (kLa) up to 2.35 s−1 and enhancement number E up to 1.387 at small gas and liquid Reynolds numbers (ReG < 5.5; ReL < 14). New predictive correlations have also been proposed by considering both the structure enhancement factor and the chemical reaction factor.