Vanadium phosphate films were deposited by a new process consisting of sequential exposures to trimethyl phosphate (TMP) plasma, O 2 plasma, and either vanadium oxytriisopropoxide [VTIP, OV(O-i-Pr) 3 ] or tetrakisethylmethylamido vanadium [TEMAV, V(NEtMe) 4 ] as the vanadium precursor. At a substrate temperature of 300 C, the decomposition behavior of these precursors could not be neglected; while VTIP decomposed and thus yielded a plasma-enhanced chemical vapor deposition process, the author found that the decomposition of the TEMAV precursor was inhibited by the preceding TMP plasma/O 2 plasma exposures. The TEMAV process showed linear growth, saturating behavior, and yielded uniform and smooth films; as such, it was regarded as a plasma-enhanced atomic layer deposition process. The resulting films had an elastic recoil detection-measured stoichiometry of V 1.1 PO 4.3 with 3% hydrogen and no detectable carbon contamination. They could be electrochemically lithiated and showed desirable properties as lithiumion battery electrodes in the potential region between 1.4 and 3.6 V versus Li þ /Li, including low capacity fading and an excellent rate capability. In a wider potential region, they showed a remarkably high capacity (equivalent to three lithium ions per vanadium atom), at the expense of reduced cyclability. V