The　structural　characteristics　involving　thermal　stabilities　of　liquid　nitromethane　(NM)—one　of　the　simplest　energetic　materials—confined　within　a　graphene　(GRA)　bilayer　were　investigated　by　means　of　all-atom　molecular　dynamics　simulations　and　density　functional　theory　calculations.　The　results　show　that　ordered　and　layered　structures　are　formed　at　the　confinement　of　the　GRA　bilayer　induced　by　the　van　der　Waals　attractions　of　NM　with　GRA　and　the　dipole–dipole　interactions　of　NM,　which　is　strongly　dependent　on　the　confinement　size,　i.e.,　the　GRA　bilayer　distance.　These　unique　intermolecular　arrangements　and　preferred　orientations　of　confined　NM　lead　to　higher　stabilities　than　bulk　NM　revealed　by　bond　dissociation　energy　calculations.　©　2015,　Springer-Verlag　Berlin　Heidelberg.