Kaolinite is widely distributed in shale formations. Kaolinite has two surface types, Si-O and Al-OH, and the two surfaces have different chemical properties. The surface wettability of kaolinite minerals is closely related to the occurrence of crude oil, the migration process of crude oil, and the filling process of crude oil. In this paper, we focus on the oil-water rock wettability of different alkane hydrocarbons on the different surfaces of kaolinite and construct a model of oil and water with variation of the alkane components on the surface of tetrahedral and octahedral kaolinite. Molecular dynamics methods were used to study the morphological changes in water clusters in different alkanes on different surfaces of kaolinite and to calculate the wetting angles. Studies have shown that the octahedral kaolinite surface is strongly hydrophilic, and the water clusters become monolayers adsorbed on the surface. Water easily displaces the oil on the surface and preferentially drives low carbon number alkanes. The tetrahedral siloxane kaolinite surface is oleophilic, the water molecules in C6H14-C18H38 are clustered on the surface, and the wetting angle of the water cluster in the alkane increases with increasing carbon number. Water has difficulty displacing oil on this surface.