Herein, we report divergent additions of 2,2'-diazidobiphenyls toward C60 and Sc3N@Ih-C80. In stark contrast to that of the previously reported bis-azide additions, the unexpected reactivity leads to the cascade dearomative formation of unprecedented azafulleroids 2 fused with a 7-6-5-membered ring system in the case of C60. In contrast, the corresponding reaction with Sc3N@Ih-C80 switches to the cascade C-H insertion pathway, resulting in multiple isomers, including a carbazole-derived [6,6]-azametallofulleroid 3 and a [5,6]-azametallofulleroid 4 and an unusual 1,2,3,6-tetrahydropyrrolo[3,2-c]carbazole-derived metallofullerene 5, whose molecular structures have been unambiguously determined by single crystal X-ray diffraction analyses. Among them, the addition type of 5 is observed for the first time in all reported additions of azides to fullerenes. Furthermore, unexpected isomerizations from 3 to 5 and from 4 to 5 have been discovered, representing the first example of isomerization from an azafulleroid to a carbazole-derived fullerene rather than an aziridinofullerene. In particular, the isomerism from [5,6]-isomer 4 to [5,6]-isomer 5 is unprecedented in fullerene chemistry, contradicting the present understanding that isomerization generally occurs between [5,6]- and [6,6]-isomers. Control experiments have been carried out to rationalize the reaction mechanism. Furthermore, representative azafulleroids have been applied in organic solar cells, resulting in improved power conversion efficiency.