A cuprous bromide-catalyzed heteroannulation reaction of [60]fullerene with ketoxime acetates has been exploited to prepare novel 1-fulleropyrrolines through the cleavage of N–O and C–H bonds and formation of C–C and C–N bonds under thermal conditions. A plausible mechanism for the formation of 1-fulleropyrrolines is proposed on the basis of the experimental results. The electrochemistry of the obtained products has also been investigated.