To summarize, our analysis reveals a decrease of the distance between the interfacial methanol molecules and the BLG layers and an enhancement in the molecular crowding at the interface when compressing between ambient pressure and 10 GPa. These factors would be in favor of a possible promotion of the BLG layers functionalization in response to an increase in pressure. By contrast, the strong intralayer H-Bond character of the interface methanol, with the OH group oriented parallel and outward with respect to the BLG layers could disfavour the BLG functionalization by reducing the outof-plane character of the O-H chemical bonds at the interface, necessary for the formation of sp 3 structures.