The fabrication of three dimensional (3D) graphene doped by Nitrogen, Boron, Ferrum and Cobalt atomics (B-N-Fe/Co-G) was demonstrated by using quick-frozen-drying and pyrolysis methods through the reactions between rGO and low cost industrial raw materials (urea, boric acid, iron nitrate, and cobalt acetate) to study the active substances of the oxygen reduction. The structure and morphology of the B-N-Fe/Co-G were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The results showed the 3D porous graphene structure of B-N-Fe/Co-G with fold surface overlapping and these atoms (N、B、Fe and Co) were equably doped in graphene. The electrocatalytic activity of the hybrid material for oxygen reduction was demonstrated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrochemical measurements indicated that the B-N-Fe/Co-G showed an initial potential around 1.0 V with four-electron reductions way and superior stability compared with 20% of the commercial Pt/C catalyst in acidic solutions.