© 2016 Elsevier Ltd Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO2(scCO2) and a prolonged depletion of residual scCO2. In this study, pore-scale scCO2dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO2into the sandstone-analogue pore network initially saturated by water without dissolved CO2(dsCO2). During the experiments, time-lapse images of dye intensity, reflecting water pH, were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO2dissolution and phase equilibrium occurs when scCO2bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO2dissolution at phase interfaces and diffusion of dsCO2at the pore scale (10–100 µm) observed after scCO2bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO2in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. This finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO2at narrow pore throats.