Replacing precious and nondurable platinum-based catalysts by economical and commercially available materials is a key issue addressed in contemporary fuel cell technology. Carbon-based nanomaterials display great potential to improve fuel tolerance and reduce the cost and stress on metal scalability. However, their relatively low catalytic activity limits the development and application of these catalysts. In this study, we have synthesized a nitrogen-doped carbon electrocatalyst from metal–organic frameworks and carbon nanotube composites, taking advantage of the existing N in the organic linker in the MOFs with more N added through ammonia treatment. The morphology and composition of synthesized catalysts were characterized by SEM, TEM, XPS, and Raman. The derived catalyst exhibited superior catalytic activity than that of commercial Pt-based catalysts. The N enriched carbon catalyst with high surface area, a graphitic carbon skeleton, and a hierarchical porous structure facilitated the mass and charge transfer during electrolysis.