Fullerene epoxides react with benzaldehyde derivatives in the presence of a pyridinium hexafluoroantimonate to give corresponding 1,3-dioxolane derivatives of [60]fullerene in excellent yields. The activation energy for the reaction of fullerene monoepoxide with benzaldehyde was determined to be 112.7 kJ mol(-1). This result shows that fullerene epoxides undergo the stepwise S-N 1-like acetalization reaction.