Platinum group metal (PGM)-free catalysts are highly desirable for oxygen reduction reaction (ORR) for clean energy. To prevent possible Fenton reaction, a catalyst containing manganese-nitrogen-carbon coordination structure (Mn-N–C) supported on monolayer graphene (Mn-N–C/G) is synthesized through a self-developed tailoring, self-assembling, and reconstructing vapor phase deposition (TSRVD) process using manganese phthalocyanine (MnPc) as the precursor. The novel catalyst Mn-N–C/G with high-density and well-organized distribution of manganese ion center coordinated with five nitrogen (Mn-N 5 ) active sites, efficient electron-conductivity from the carbon six-member ring, and ideal structural stability shows an onset potential of 0.99 V vs. RHE and current density of 1.3 mA cm −2 at potential 0.88 V vs. RHE compared with commercial Pt/C (0.96 V vs. RHE and 1.1 mA cm −2 , respectively). Based on the analyses of SEM, HRTEM, XRD, SAED, Raman, and XPS on catalyst Mn-N–C/G, a reasonable formation model of catalyst Mn-N–C/G is proposed.