Plasma Enhanced Chemical Vapor Deposition (PECVD) was used to prepare vanadium oxide thin films as cathodes for rechargeable lithium batteries. The reactants consisted of a high vapor pressure liquid source of vanadium (VOCl3) and hydrogen and oxygen gas. Deposition parameters such as the flow rates of H2, O2 and VOCl3, the substrate temperature and the Rf power were optimized, and high deposition rate of 11 Å/s was obtained. Vanadium oxide films with high discharge capacities of up to 408 mAh/g were prepared. The films also showed a superior cycling stability between 4 and 1.5 V at a C/0.2 rate for more than 4400 cycles. The films were amorphous up to a deposition temperature of 300°C, however, deposition on to substrates with textured surfaces facilitated the formation of crystalline films. We demonstrate that both the vanadium oxide material and the PECVD deposition method are very attractive for constructing thin-film rechargeable lithium batteries with high capacity and long-term cyclic stability.