3D Boron and Nitrogen dual-doped graphene and carbon nanotubes (B-N-G-CNTs) was fabricated by chemical vapour deposition (CVD) method. The structure and morphology of the B-N-G-CNTs were investigated by scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and transmission electron microscopy (TEM). The results showed that the B-N-G-CNTs were of 3D porous graphene structure, the graphene and carbon nanotubes formed into a stable chemical bonding, showing the features of high quality and less defects. The electrocatalytic activity for oxygen reduction was demonstrated by cyclic voltammetry (CV), the rotating disk electrode (RDE) and Amperometeic (i-t curve) method. The electrochemical measurements showed the B-N-G-CNT was more efficient than B-N-G for ORR in terms of the onset/peak potential while a typical four-step pathway was seen for the B-N-G-CNT in an O2-saturated 0.1mol·L-1 KOH solution, and the catalytically active sites on the B-N-G-CNTs were much more durable than the commercial Pt/C electrode.