Covalent　organic　frameworks　(COFs)　are　promising　materials　for　converting　solar　energy　into　green　hydrogen.　However,　limited　charge　separation　and　transport　in　COFs　impede　their　application　in　the　photocatalytic　hydrogen　evolution　reaction　(HER).　In　this　study,　the　intrinsically　tunable　internal　bond　electric　field　(IBEF)　at　the　imine　bonds　of　COFs　was　manipulated　to　cooperate　with　the　internal　molecular　electric　field　(IMEF)　induced　by　the　donor-acceptor　(D-A)　structure　for　an　efficient　HER.　The　aligned　orientation　of　IBEF　and　IMEF　resulted　in　a　remarkable　H2　evolution　rate　of　57.3　mmol·g–1·h–1　on　TNCA,　which　was　approximately　520　times　higher　than　that　of　TCNA　(0.11　mmol·g–1·h–1)　with　the　opposing　electric　field　orientation.　The　superposition　of　the　dual　electric　fields　enables　the　IBEF　to　function　as　an　accelerating　field　for　electron　transfer,　kinetically　facilitating　the　migration　of　photogenerated　electrons　from　D　to　A.　Furthermore,　theoretical　calculations　indicate　that　the　inhomogeneous　charge　distribution　at　the　C　and　N　atoms　in　TNCA　not　only　provides　a　strong　driving　force　for　carrier　transfer　but　also　effectively　hinders　the　return　of　free　electrons　to　the　valence　band,　improving　the　utilization　of　photoelectrons.　This　strategy　of　fabricating　dual　electric　fields　in　COFs　offers　a　novel　approach　to　designing　photocatalysts　for　clean　energy　synthesis.　©　2024　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences