Na1/2Bi1/2TiO3-based materials have gained considerable attention for their potential to exhibit giant strain, very-high ionic conductivity comparable to yttria stabilized zirconia or high mechanical quality factor for use in high power ultrasonics. In recent times, quenching Na1/2Bi1/2TiO3-based compositions have been demonstrated to enhance the thermal depolarization temperature, thus increasing the operational temperature limit of these materials in application. This work investigates the role of quenching-induced changes in the defect chemistry on the dielectric, ferroelectric and piezoelectric properties of quenched Na1/2Bi1/2TiO3-BaTiO3. The quenched samples indeed demonstrate an increase in the bulk conductivity. Nevertheless, while subsequent annealing of the quenched samples in air/oxygen atmosphere reverts back the depolarization behaviour to that of a furnace cooled specimen, the bulk conductivity remains majorly unaltered. This implies a weak correlation between the defect chemistry and enhanced thermal stability of the piezoelectric properties and hints towards other mechanisms at play. The minor role of oxygen vacancies is further reinforced by the negligible (10–15%) changes in the mechanical quality factor and hysteresis loss.