Our study provides a detailed microscopic insight into the structure and reactivity of the bilayer graphene (BLG)/methanol interface at room temperature under varying pressure conditions. A study of the interface in terms of structural descriptors has allowed to characterize the structural evolution of interface, showing a decreasing trend in the methanol-graphene distance up to 2.9 GPa, beyond which the distance stabilizes and remains constant up to 10 GPa. Additionally, we observed a gradual reduction in the carbon-carbon interlayer distance, accompanied by increased molecular crowding for increasing pressure. Notably, a strong intralayer H-bond character of the interface methanol, with the OH group oriented parallel and outward with respect to the BLG layers at high pressure, has also been identified.