Currently, transition metal oxides are widely explored as electrode materials for lithium ion batteries due to their remarkably large reversible capacities. However, these materials always suffer from poor conductivities and slow lithium ion diffusion in the lattice. Given this, a distinctive 3D porous network is developed through partial exfoliation of multiwall carbon nanotubes, which can function as not only superior conductive additive but also as an efficient 3D porous scaffold. By self-assembling with V₃O₇·H₂O nanowires, the hybrid electrode is demonstrated to achieve a significant boost in lithium storage when compared with pristine V₃O₇·H₂O nanowires. This method can provide much inspiration in the construction of high-performance metal oxides based electrodes.