A lead(IV) acetate-promoted radical reaction of [60]fullerene with halocarboxylic acids has been exploited to synthesize rare ortho acid ester-type 1,3-dioxolanofullerenes, the hydroxyl group of which can be further transformed to an ester or ether group. Intriguingly, an ortho acid ester-type 1,3-dioxolanofullerene can also be converted to a 1,4-dioxanonofullerene in the presence of a base or manipulated to another ortho acid ester-type 1,3-dioxolanofullerene by reaction with a stronger halocarboxylic acid. Moreover, two possible reaction pathways leading to the observed products are also proposed.