Comprehensive SummaryA series of unreported fullerodihydropyridine‐3‐ones were synthesized as a new family of fullerene derivatives in moderate to good yields by a simple one‐step reaction of [60]fullerene with cheap and readily available β‐substituted ethylamines in the absence or presence of arylacetaldehydes under the assistance of Cu(OAc)2. The in situ generation of arylacetaldehydes by the C—N bond cleavage of arylethylamines avoided their complex synthesis in advance and realized the preparation of fullerodihydropyridine‐3‐ones with structural and functional diversities, which may have promising applications in perovskite solar cells to improve the performance of photovoltaic devices due to the existence of a large π‐conjugated system on the dihydropyridine‐3‐one ring.