Transition-metal-salt-mediated radical reactions of fullerenes have attracted extensive attention as a new and important method for fullerene functionalization.The application of relatively cheap and easily available ferric perchlorate(Fe(ClO4)3) to the synthesis of [60]fullerene(C60) has demonstrated remarkable advantages and afforded a series of novel fullerene derivatives.In this review we present our recent progress in this area and summarize the reactions of C60 with malonate esters,β-keto esters,nitriles,aldehydes/ketones,and arylboronic acids in the presence of Fe(ClO4)3 to afford the C60-fused disubstituted lactones,C60-fused hemiketal,C60-fused dihydrofuran,C60-fused oxazoles,C60-fused 1,3-dioxolanes,and fullerenyl boronic esters.The possible reaction mechanisms for the above-mentioned reactions are also described in detail. Transition-metal-salt-mediated radical reactions of fullerenes have extensive extensive attention as a new and important method for fullerene functionalization. The application of relatively cheap and easily available ferric perchlorate (Fe (ClO4) 3) to the synthesis of [60] fullerene This review we present our recent progress in this area and summarize the reactions of C60 with malonate esters, β-keto esters, nitriles, aldehydes / ketones, and arylboronic acids in the presence of Fe (ClO4) 3 to afford the C60-fused disubstituted lactones, C60-fused hemiketal, C60-fused dihydrofuran, C60-fused oxazoles, C60-fused 1,3-dioxolanes, and fullerenyl boronic esters. reaction mechanisms for the above-mentioned reactions are also described in detail.