To overcome the ever-growing organic pollutions in the water system, abundant efforts have been dedicated to fabricating efficient Fenton-like carbon catalysts. However, the rational design of carbon catalysts with high intrinsic activity remains a long-term goal. Herein, we report a new N-molecule-assisted self-catalytic carbonization process in augmenting the intrinsic Fenton-like activity of metal–organic-framework-derived carbon hybrids. During carbonization, the N-molecules provide alkane/ammonia gases and the formed iron nanocrystals act as the in situ catalysts, which result in the elaborated formation of carbon nanotubes (in situ chemical vapor deposition from alkane/iron catalysts) and micro-/meso-porous structures (ammonia gas etching). The obtained catalysts exhibited with abundant Fe/Fe–Nx/pyridinic-N active species, micro-/meso-porous structures, and conductive carbon nanotubes. Consequently, the catalysts exhibit high efficiency toward the degradation of different organic pollutions, such as bisphenol A, methylene blue, and tetracycline. This study not only creates a new pathway for achieving highly active Fenton-like carbon catalysts but also takes a step toward the customized production of advanced carbon hybrids for diverse energy and environmental applications.