The　efficiency　and　stability　of　perovskite　solar　cells　(PSCs)　can　be　greatly　affected　by　various　factors　such　as　passivating　the　perovskite　film,　oxidizing　the　hole-transport　material　of　2,2′,7,7′-tetras(N,N-p-methoxyaniline)-9,9′-spirodifluorene　(Spiro-OMeTAD),　and　inhibiting　the　iodide　migration.　Here　we　introduce　a　multifunctional　starch-iodine　complex　in　the　perovskite　film　to　enhance　the　fill　factor　and　stability　of　PSCs.　Results　demonstrate　that　the　starch-iodine　complex　from　the　perovskite　film　can　release　iodine　molecules　to　gently　oxidize　the　Spiro-OMeTAD,　which　can　significantly　increase　the　PSC＇s　fill　factor.　Moreover,　the　remaining　starch　can　effectively　passivate　the　perovskite　film　to　obviously　improve　the　PSC＇s　long-term　stability.　Furthermore,　the　starch-iodine　complex　can　absorb　and　store　the　iodide　ions　to　generate　a　starch-triiodide　complex,　which　can　release　iodide　ions　to　promote　iodide　defect　self-healing　and　suppress　iodide　migration　in　the　perovskite　films,　resulting　in　a　further　enhancement　of　the　PSC＇s　long-term　stability.　As　a　result,　the　PSC　based　on　the　starch-iodine　complex　obtains　a　superior　cell　efficiency　of　22.60%　with　a　high　fill　factor　of　79.54%,　and　keeps　91.12%　of　its　original　efficiency　after　1500　h.　©　2024　Elsevier　B.V.