A mild and facile process for the preparation of 1,4-fullerenols C(60)ArOH was achieved. The key intermediate 1,2-C(60)Ar(NO(2)) was identified to better understand the reaction mechanism. Further functionalizations including esterification, etherification, and arylation of the synthesized 1,4-C(60)ArOH provided efficient access to versatile fullerene derivatives in the presence of p-toluenesulfonic acid.