In the context of carbon sequestration in saline aquifers, we investigate CO2 transport dynamics in brine under reservoir-like conditions (P = 8 MPa, T = 50∘C) using microfluidics. We quantify the mass transfer of supercritical CO2 in brine across a range of concentrations (0–1 M) and liquid flow rates (15–60 μL/min) for the first time. We find the volumetric mass transfer coefficient kLa ranges from 50.3 to 144.0 s−1, increasing with flow rate and, to a lesser extent, with salinity. More importantly, the kLa value for supercritical CO2 in brine at a higher temperature shows a significant enhancement of >50% compared to gas and liquid CO2 in water. Our analysis, incorporating a theoretical mass transfer model, points to a dominant contribution from the liquid film to the overall kLa, nearly doubling that of the emulsion caps, attributed to the thin film's larger surface area and dynamic renewal.