A series of N‐unsubstituted/substituted fullerotetrahydroquinolines without a directly attached nitrogen atom were synthesized in moderate to good yields via a one‐pot two‐step reaction of [60]fullerene with arylamines and paraformaldehyde in the presence of trifluoromethanesulfonic acid and p‐toluenesulfonic acid monohydrate. Aromatic primary amines produce N‐unsubstituted fullereotetrahydroquinolines, while aromatic secondary amines give N‐substituted fullereotetrahydroquinoline derivatives. As precursors, N‐unsubstituted fullerotetrahydroquinolines could be further derivatized by the N‐alkylation/acylation/carboamidation reactions to produce a large variety of N‐substituted fullerotetrahydroquinolines containing Cl, NO2, C(O), and C(O)NH functional groups, which may have applications in the field of perovskite‐based solar cells. Plausible reaction pathways for the formation of N‐unsubstituted/substituted fullerotetrahydroquinolines were suggested to elucidate the above‐mentioned reaction process.