The　electronic　structure　and　reactivities　of　Fe(CO)n　(n　=　3∼5)　addition　to　different　fullerenes　have　been　investigated　through　the　first-principles　calculations,　and　the　results　indicate　that　Fe(CO)3　and　Fe(CO)4　can　be　adsorbed　to　the　outside　network　of　fullerene　via　hollow　and　bridge　sites,　respectively.　Both　of　them　have　larger　binding　energy,　but　when　Fe(CO)5　is　adsorbed　via　the　top　site,　the　binding　energy　is　relatively　smaller.　According　to　the　directional　curvature　theory,　the　reactivities　of　Fe(CO)3　addition　to　the　fullerenes　are　determined　by　KM　of　the　ring　center,　and　those　of　Fe(CO)4　addition　by　KD　of　the　C-C　bond　curvature;　while　for　Fe(CO)5,　it　presents　weak　reactivities　in　the　addition　reaction　because　of　the　larger　volume　effect.　No　matter　whether　the　addition　reaction　takes　place　on　the　hollow　or　bridge　site,　the　binding　energies　show　a　linear　relationship　with　KD.　This　work　further　enriched　the　directional　curvature　theory　and　applied　the　isolobel　analogy　theory　in　the　fullerene　addition　reactions.