In this paper, three-dimensional (3D) graphene network was prepared by chemical vapor deposition (CVD) on 3D porous Ni template. The as-prepared 3D graphene showed high conductivity of ∼600Scm−1 and low square resistance of 1.6Ωsq−1. With the aid of 3D graphene network, the poorly conductive LiFePO4 exhibited high conductivity and good rate performance of 109mAhg−1 at 10C, indicating potential application in high rate lithium ion batteries.