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)-　＇　,7,7　＇-tetras(N,N-　p-methoxyaniline)-　9,9　＇-spirodifluorene　＇-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　SpiroOMeTAD,　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.