Non-platinum group metal (non-PGM) catalysts have a huge potential in many electrochemical systems such as fuel cells due to the high raw material cost of PGM catalyst. However, there is a significant gap between the current level of electrochemical performance of non-PGM catalysts and that of PGM catalysts. Nitrogen doped-Graphene/MOF (N-G/MOF), a new high performance non-PGM catalyst which was synthesized by high energy wet ball milling with graphene oxide, melamine, and Metal organic framework material as raw materials, was investigated in this research. The physical, chemical, structural and electrochemical properties of new synthesized N-G/MOF catalysts were characterized by XPS, FTIR, SEM-EDS, TEM, XRD, RRDE and fuel cell testing station. The comparison between properties of N-G/MOF, N-G (without MOF), and MOF (without N-G) shows that N-G/MOF has better electrochemical performance than both N-G and MOF. Furthermore, the catalytic mechanism of N-G/MOF catalysts was investigated in this research. The successful accomplishment of the new MOF-based catalytic materials and the understanding of the mechanism provide the substantial way to the cost-effective and fuel-efficient energy conversion system.