The facile one-step reaction of [60]fullerene with isocyanates/isothiocyanates in the presence of ferric perchlorate generates a series of oxazolidinofullerenes/thiazolidinofullerenes, which are difficult to prepare by common methods. The direct dissolution approach plays an important role in the efficient synthesis of oxazolidinofullerenes/thiazolidinofullerenes. A possible reaction mechanism for the product formation is proposed.