AlN thin films were deposited on c-, a- and r-plane sapphire substrates by the magnetron sputtering technique. The influence of high-temperature thermal annealing (HTTA) on the structural, optical properties as well as surface stoichiometry were comprehensively investigated. The significant narrowing of the (0002) diffraction peak to as low as 68 arcsec of AlN after HTTA implies a reduction of tilt component inside the AlN thin films, and consequently much-reduced dislocation densities. This is also supported by the appearance of E₂(high) Raman peak and better Al–N stoichiometry after HTTA. Furthermore, the increased absorption edge after HTTA suggests a reduction of point defects acting as the absorption centers. It is concluded that HTTA is a universal post-treatment technique in improving the crystalline quality of sputtered AlN regardless of sapphire orientation.