Polymeric　carbon　nitride　(PCN),　also　called　melon,　is　a　well-studied　nonmetal　catalyst　in　the　field　of　photocatalysis,　while　the　nature　of　charge　transport　in　PCN　has　not　been　thoroughly　unveiled　at　the　microscopic　level.　In　this　work,　we　have　combined　density　functional　theory　(DFT)　and　nonadiabatic　dynamics　(NAMD)　simulations　to　investigate　the　effect　of　interlayer　interactions　on　the　dynamic　properties　of　photogenerated　carriers　of　melon.　Overall,　the　interlayer　π-π　interaction　has　a　greater　effect　on　hot　electrons　than　on　holes,　which　accelerates　the　relaxation　of　electrons　in　bulk　melon.　In　both　monolayer　and　bulk　melon,　electrons　and　holes　have　the　same　antibonding　π　bond　characteristics,　which　drives　the　separation　of　charges.　However,　due　to　the　strong　π-π　stacking,　carriers　in　bulk　melon　can　transfer　and　separate　between　layers,　causing　the　much　longer　nonradiative　recombination　of　charge　carriers　in　bulk　than　that　in　monolayer,　which　makes　melon　have　a　long　carrier　lifetime　and　exhibit　photoelectric　performance　similar　to　that　of　inorganic　semiconductors.　©　2023　American　Chemical　Society.