The structure-driven properties of vanadium oxide have inspired enormous developments in the last decades, especially as a smart material for energy, sensors, and optoelectronics. The large variety of stable and metastable structures of vanadium oxide is discussed, based on the calculated formation energies and a broad overview of their structure-related properties. The established chemical deposition processes from the gas phase are reviewed with a particular emphasis on the implemented precursors and the obtained vanadium oxide phases. Although a significant fraction of relevant vanadium oxide compounds is achieved by these methods, there are still rewarding challenges related to their controlled elaboration and the investigation of their responsive properties.