The facile one-step reaction of [60]fullerene with various diols in the presence of ferric perchlorate afforded a series of rare fullerene-fused dioxanes/dioxepanes. Nevertheless, the reaction of [60]fullerene with diethylene glycol, triethylene glycol, and tripropylene glycol promoted by ferric perchlorate unexpectedly generated fullerene-fused dioxanes instead of the anticipated fullerene-fused crown ethers. A plausible reaction mechanism is proposed to explain the formation of fullerene-fused dioxane/dioxepane products.