LiNi1/3Co1/3Mn1/3O2/Ag composite cathodes are synthesized by a thermal decomposition method and multi-walled carbon nanotubes are uniformly introduced into the composites through ball mixing. A composite electrically conductive network consisting of CNTs and Ag is obtained to improve the conductivity of LiNi1/3Co1/3Mn1/3O2 material. By comparing with the pure LiNi1/3Co1/3Mn1/3O2 and cathode modified by CNTs or Ag, the as-obtained LiNi1/3Co1/3Mn1/3O2–CNT/Ag electrode exhibits the best rate capability (120.6mAh/g at 5C) and cycle performance (134.2mAh/g at 1C with a capacity retention of 94.4% over 100 cycles). With the construction of 3D spatial conductive network, the novel hybrid CNT/Ag demonstrates itself a promising strategy to improve Li storage performance for lithium ion batteries.