The　migration　and　volatilization　of　cations　within　organic–inorganic　hybrid　perovskite　(OIPs)　materials　has　been　identified　as　a　major　issue　for　irreversibly　degrading　perovskite　solar　cells　(PSCs),　severely　limiting　their　performance　and　impeding　progress　toward　large-scale　applications.　To　mitigate　these　problems,　an　adjustable　cation　immobilization　strategy　was　proposed　for　the　first　time,　in　which　a　series　of　fluorobenzenesulfonamide　(FBSA)　molecules　was　introduced　into　perovskite　precursor,　a　strong　coordination　bond　was　formed　between　the　sulfonamide　group　with　the　octahedral　imperfection　caused　by　iodine　vacancy,　along　with　a　hydrogen　bond　formed　between　the　cation　and　F　atom.　As　a　result,　the　A-site　cations　were　tightly　immobilized　in　the　octahedral　of　perovskite　crystal　lattice　and　the　uncoordinated　Pb2+　defects　were　effectively　eliminated.　Besides,　the　immobilization　distance　of　cation　was　finely　optimized　by　changing　the　substitution　position　of　F　atoms.　Based　on　the　cation-immobilized　perovskite　film,　the　efficiency　of　PSCs　was　significantly　increased　from　19.88　%　to　22.30　%.　Moreover,　the　unencapsulated　PSCs　exhibited　impressive　light　and　thermal　stability,　retaining　82　%　of　the　initial　efficiency　after　720　h　illumination　at　1-sun,　and　maintaining　nearly　80　%　of　the　initial　PCE　after　heating　at　85　°C　for　240　h.　Thus,　the　present　study　offers　a　promising　approach　for　advancing　the　commercialization　of　stable　and　high-efficiency　perovskite　solar　cells.　©　2024　Elsevier　B.V.