Geological carbon sequestration (GCS) is a promising method to alleviate CO2 emission, while CO2 structural trapping is one of main GCS mechanisms, in which the storage capacity is strongly dependent on CO2-water–rock contact angle. Although CO2-water-kaolite contact angle on basal surfaces has been studied, the knowledge about kaolinite edge surface wettability remains unknown. In this work, we use molecular dynamics (MD) simulations to study CO2-water-kaolinite contact angle on kaolinite gibbsite and edge surfaces under a typical GCS condition (330 K and 200 bar). The common belief is that surface wettability in presence of water is determined by surface hydroxyl (–OH) group density. While the surface –OH group density of kaolinite edge surface is much lower than that of gibbsite surface, both gibbsite and edge surfaces are strongly water-wet. Edge surface is better hydrated than gibbsite surface as both silanol and aluminol groups can form hydrogen bonding with water molecules thanks to large effective water accessible volume around them, while pocket water can further anchor water film. Therefore, the atomic-level surface characteristics dictate interfacial water structures which determine CO2-water-kaolinite contact angle. Our study provides important insights into the effect of surface heterogeneity on interfacial water structures, and kaolinite gibbsite and edge surface wettability which is crucial to the optimization of GCS processes.