Ag/β-AgVO3 hybrid nanorods have been successfully prepared by a facile one-step solid-state approach and their electrochemical performance has been evaluated as cathode materials for lithium batteries (LBs). The effects of calcinations temperatures to the morphologies of the material and the content of Ag in the hybrid have been investigated. The Ag/AgVO3 hybrid synthesized at 420 °C shows well-separated nanorods anchored with Ag nanoparticles. The existence of Ag nanoparticles has been demonstrated to improve the conductivity of the electrode. As a cathode material for lithium batteries, it exhibits high specific capacity, good rate capability and improved cycle stability. Initial specific discharge capacities of 242, 228, 203, 202, 198 mA h g−1 can be achieved at the current densities of 50, 100, 200, 400, 800 mA g−1, respectively. The superior performance is attributed to the combined effect of the electron conductivity improvement by the Ag nanoparticles and the well-separated β-AgVO3 nanorod structures. The results demonstrate the advantages of the Ag/AgVO3 hybrid for primary lithium batteries, and the possible application in rechargeable lithium batteries.