Given the unique properties of sewage sludge-derived carbonaceous materials (SC) and the correlation of SC with recycling sewage sludge in an efficiently safe way, there is significant attraction from researchers to develop innovative methodologies that enable a more extensive application of SC. Applying SC in forming rather than cleaving chemical bonds is highly desirable to maximize the value of sewage sludge. Here, we report the surface-modified SC-catalyzed N-H insertion reaction of a wide range of alpha-aryl diazoesters with amines, which was first accomplished with moderate to good yield (86%). The catalytic performance of this catalyst is shown by a 10 gram-scale reaction and the synthesis of a drug molecule, (+/-)-clopidogrel. A mechanistic study suggests that the C-N bond formation involves ammonium ylide intermediates and hydrogen bonding. This discovery leads to the realization of a feasible strategy for sewage sludge recycling and a new avenue to catalyst research.