Physical vapor deposition method was used for the preparation of nanostructured TeO₂. Different morphologies of TeO₂ are synthesized using a physical evaporation method with Te powder as the source material and quartz SiO₂ as the growth substrates. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and ultravioletvisible (UV–Vis) analyses are used to characterize the structural, morphological, and optical properties of the TeO₂ products obtained. By varying the annealing temperature, different morphology of TeO₂ structuresis investigated. TeO₂ nanostructure progress is initiated by the crystallization of particles. Different temperatures have different effects on structures, which are discussed. The films as deposited nature was amorphous; crystallization occurred at a higher annealing temperature (175°C). With an increase in annealing temperature, the TeO₂ films grain size increased. The research also points to the impact of post-deposition thermal annealing temperatures in excess of 100 °C in enhancing TeO₂ film characteristics.