Vanadium oxide nanostructured thin films (NTFs) are synthesized using plasma assisted sublimation process (PASP) in different gases' Ar, O2, and N2 plasma (AP, OP, and NP) and O2 gas (OG) ambient. Morphological studies conducted via electron microscopy reveal nanostrips, nanoflakes, nanorods, and nanoparticles organized as clusters for OP, OG, AP, and NP respectively. X‐ray photoelectron spectroscopy (XPS) studies show that samples OP and OG are composed of α‐V2O5, whereas AP and NP are composed of V6O13 along with V2O5. The relative percentages calculated using XPS data show that in AP, V6O13, and V2O5 are 38 and 62%, respectively. These percentages change to 48% for V6O13 and 52% for V2O5 in NP. The V6O13/V2O5 ratio is lower in AP than NP. This increment of V6O13 in NP is due to presence of more reductive species in N2 plasma than Ar plasma. Since N2 plasma contains species like N*, , etc. it leads to the formation of NO2, N2O, etc. Raman spectra indicate the surface of the sample NP consisting of both V6O13 and V2O5, agreeing with the X‐ray diffraction (XRD) and XPS results. Studies demonstrate that plasma ambient during synthesis process affects both morphology and composition of deposited vanadium oxide NTFs.