Poly(triazine　imide)·Li+Cl-　(PTI/Li+Cl-)　as　one　of　the　most　reported　crystalline　carbon　nitrides　has　shown　exciting　potential　for　photocatalysis.　However,　understanding　the　role　of　Li+/Cl-　in　the　photoexcited　charge　transfer　in　the　time　and　space　of　PTI　is　a　challenging　problem.　Here,　we　have　investigated　the　nonradiative　charge　recombination　of　series　ion　intercalated　PTI　systems　(PTI/Li+X-,　where　X　=　F,　Cl,　Br,　and　I)　by　performing　the　ab　initio　nonadiabatic　molecular　dynamics　simulations.　The　results　indicate　that　the　intercalated　anions　in　PTI/Li+Cl-　and　PTI/Li+Br-　have　the　potential　to　trap　holes,　separate　the　electrons　and　holes,　and　prolong　the　nonradiative　electron-hole　recombination.　In　particular,　∼70%　of　holes　in　PTI/Li+Cl-　can　transport　among　interlayers　toward　the　{0001}　planes,　while　most　of　the　electrons　are　transferred　to　the　{101̅0}　planes,　exhibiting　different　transport　pathways　and　directions.　Furthermore,　PTI/Li+Cl-　has　an　electron-hole　recombination　time　as　long　as　136　ns,　which　explains　its　excellent　optoelectronic　properties.　This　work　provides　a　theoretical　baseline　for　the　reported　facet　engineering　improvement　of　crystalline　carbon　nitride　for　overall　water　splitting.　©　2024　The　Authors.　Published　by　American　Chemical　Society.