Correlation of structural, vibrational, and optical properties with the oxygen ion conductivity mechanism in Ca and Mg single and co-doped LaAlO 3 solid electrolytes synthesized via the sol−gel technique has been explored in the intermediate temperature range of 350−700 °C. The disordering of oxygen vacancies has been analyzed through temperature-dependent Raman spectroscopy in doped LaAlO 3 . Faster disordering of oxygen defects associated with AlO 6 octahedra and LaO 12 dodecahedra has been observed in lesser distorted samples (higher Ca content) with temperature, but at the same time, the defect concentration of oxygen vacancies crucially impacts the ionic conductivity mechanism. Experimental evidence of oxygen and anti-site defects has been probed through optical absorption spectroscopy in the diffused reflectance mode, wherein the temperaturedependent diffuse reflectance spectra indicate the delocalization of oxygen vacancies and anti-site defects above 250 and 300 °C, respectively. Comprehensively, temperature-dependent Raman and optical absorption spectroscopies have emerged as influential techniques for probing the signature of disordering and delocalization of oxygen vacancies and anti-site defects in solid-state oxidebased materials.