Phase-change memory emerges as a top contender for non-volatile data storage applications. We report here a systematic change in local structure and crystallization kinetics of binary GeTe thin films using temperature-dependent resistivity measurements, which offers single-stage crystallization at around 187 °C, corroborated with x-ray diffraction. Furthermore, the change in chemical bonding upon crystallization is determined through x-ray photoelectron spectroscopy core level spectra, which reveals the existence of Ge and Te components that align with the GeTe crystal structure. Also, an investigation was carried out employing a UV–Vis–NIR spectrophotometer to explore the evolution of optical bandgaps (Eg), Tauc parameter (B) representing the local disorder, and Urbach energy (Eu) of the GeTe material, as it undergoes the transition from a disordered amorphous state to a crystalline state. As crystallization progresses, a consistent shift of Eg from 0.92 to 0.70 eV corresponds to as-deposited amorphous at room temperature and crystalline at 250 °C, respectively. In addition, the reduction in Eu (from 199.87 to 141.27 meV) and a sudden increase of B around crystallization temperature is observed upon increasing temperature, indicating direct observation of enhanced medium-range order and distortion in short-range order, respectively, in GeTe thin films, revealing improved structural and optical properties. These enhancements make the GeTe material ideal for data storage applications of phase-change memory for next-generation computing technology.