Perovskite　solar　cells　(PSCs)　efficiency　has　recently　achieved　significant　advancements,　surpassing　the　26%　threshold.　Excessive　PbI2,　often　used　in　high-efficiency　PSCs,　will　also　cause　stability　or　defect　problems.　To　address　these　challenges,　we　introduce　anionic　and　cationic　bifunctional　additives　to　passivate　PSCs　synergistically.　Phenylethylamine　trifluoroacetate　(PEATFA)　is　utilized　as　an　additive　to　passivate　the　perovskite　film.　The　PEA(+)　cation　facilitates　the　formation　of　two-dimensional　perovskite　while　TFA(-)　anion　passivate　the　uncoordinated　Pb2+　ions　and　iodine　vacancies,　enhancing　perovskite　crystal　quality　without　excess　PbI2.　Furthermore,　PEATFA　modification　optimizes　the　energy　level　matching　between　the　perovskite　and　charge　transfer　layers,　thereby　enhancing　charge　transfer　and　extraction　capabilities.　Finally,　the　device　achieves　an　impressive　power　conversion　efficiency　of　24.05%　while　exhibiting　minimal　hysteresis　and　good　stability.