Phase-selective synthesis of crystalline vanadium oxides is achieved by the CVD of vanadium oxo-tri-isopropoxide [VO(OiPr)3]. Preformed V-O and V=O units and their differential thermal stability present in the precursor enabled precise modulation of the vanadium/oxygen stoichiometry in the products of the CVD. No additional oxygen carrier is employed during the deposition processes. Subject to deposition temperature (400-700 °C), different phase compositions (V2O5, V7O13, and VO2) are directly obtained and are investigated regarding structural and electrical properties. Hall measurements on VO2films show a sharp metal-to-semiconductor transition at 78 °C (single crystal, 68 °C) depending on their microstructure formed by an oriented aggregation of individual crystallites.