Pristine　graphene　is　widely　considered　to　be　chemically　inert,　but　recent　experimental　studies　have　suggested　that　it　can　provide　frustrated　Lewis　pairs　(FLPs)　for　activating　H2under　mild　conditions.　Using　density　functional　theory　(DFT)　and　ab　initio　molecular　dynamics　(AIMD)　calculations,　we　explore　in　this　work　the　possibility　that　corrugation　in　pristine　graphene　is　responsible　for　the　formation　of　FLPs　and　thus　its　observed　catalytic　activity.　Our　DFT　results　demonstrate　that　the　ease　of　H2activation　is　proportional　to　the　degree　of　corrugation　of　graphene.　For　corrugated　graphene,　the　two　catalytic　para-carbon　sites　show　clear　signs　of　transient　Lewis　acid/base　properties　along　the　reaction　coordinate,　a　pre-requisite　for　FLPs.　Furthermore,　the　two　dissociating　H　atoms　carry　opposite　charges,　suggesting　heterolytic　activation　of　H2.　This　behavior　is　confirmed　by　AIMD　simulations　at　room　temperature,　which　show　that　fluctuations　of　the　corrugated　graphene　lead　to　C　sites　with　diverse　distances　and　varying　charges.　These　observations　offer　a　plausible　rationalization　of　the　experimental　observations　and　possible　design　principles　for　FLP　catalysts　using　homogeneous　two-dimensional　materials.　©　2022　American　Chemical　Society.　All　rights　reserved.