A general and facile annulation of various diol motifs to [60]fullerene has been developed. This protocol can afford not only 6- to 10-membered-ring fullerenyl diethers in one step from simple acyclic diols but also directly couple [60]fullerene with a variety of structurally diverse sugars. The [60]fullerene-sugar conjugates formed do not require any linker moiety and maintain their inherent structural integrity. The electrochemistry of the fullerenyl diethers and [60]fullerene-sugar conjugates has also been investigated.