Considering the high anisotropy in the compression both of graphite as well as of bilayer graphene we have investigated BLG immersed in methanol exposed to increasing out-of-plane pressure (i.e., the P zz component of the stress tensor) from 0.0001 to 10 GPa, while keeping the in-plane pressure to the ambient value (0.0001 GPa). Experimentally, methanol is liquid below 3.5 GPa, while it forms an amorphous solid above 3.5 GPa. The first part of our study exploits DFT-MD simulations performed on models pre-equilibrated with classical MD. The main goals are i) to provide a microscopic characterization of the BLG/methanol interfaces as a function of pres-sure, shedding light on the link between interface structure and reactivity; ii) to observe BLG functionalization and/or formation of C-C covalent inter-layer bonds (sp 2 → sp 3 transformations) at high-pressure.