Fullerene mixed peroxides C60(t-BuOO)6 and C60(O)(t-BuOO)6 react with Lewis acids to form variousfullerenols through the partial fragmentation of t-BuOO groups. Two monohydroxyl fullerenols with thegeneral formula C60(OH)(t-BuOO)5 and six monohydroxyl fullerenols with the general formula C60(O)(OH)(t-BuOO)5 were prepared, which are essentially the same except the location of the OH group. Anadditional reaction of the monohydroxyl fullerenols gave bis- and trishydroxyl fullerenols. Single-crystalX-ray structures have been obtained for the two monohydroxyl fullerenols. Other compounds arecharacterized by chemical correlation and their spectroscopic data. Cuprous bromide could protect themost reactive t-BuOO group from being attacked by stronger Lewis acids. The proposed mechanismmainly involves Lewis acid induced heterolysis of the peroxo O−O bond.