The photochemical reactions of C60 with N-(trimethylsilyl)methyl substituted and N-alkyl/aryl substituted α-aminonitriles were explored to evaluate the scope and reaction efficiency depending on the structural nature of amine substrates. The results showed that photoreactions of C60 with trimethylsilyl group containing N-alkyl amines produced predominantly both trimethylsilyl and cyano group containing trans-pyrrolidine ring fused fulleropyrrolidines in a chemo- and stereoselective manner. Interestingly, photoreactions of C60 with N-branched alkyl substituted amines led to exclusive formation of non-silyl containing cycloadducts. In contrast to those of N-alkyl substituted α-aminonitriles, photoreactions of N-(trimethylsilyl)methyl and N-aryl substituted α-aminonitriles gave rise to the formation of both trans- and cis-isomeric fulleropyrrolidines with an inefficient and non-stereoselective manner. The feasible mechanistic pathways leading to generation of fulleropyrrolidines are 1,3-dipolar cycloaddition of the azomethine ylides, generated by either a single electron transfer (SET) (under N2-purged conditions) or H atom abstraction (under O2-purged conditions) process, to fullerene C60. The stereoselectivities of photoproducts depending on the nature of amines are likely to be associated with conformational stabilities of in situ generated azoemthine ylides.