The epitaxial quality of AlN grown on sapphire substrate by metalorganic vapor phase epitaxy (MOVPE) is improved upon the incorporation of nanometer‐thin amorphous Al2O3 interlayer by atomic layer deposition (ALD). The critical ALD‐Al2O3 thickness is determined to be around 1 nm, where the AlN exhibits a parallel step‐and‐terrace surface morphology. However, with increasing ALD‐Al2O3 thickness, the surface changes to meandering step‐and‐terrace morphology due to the formation of surface defects in the ALD‐Al2O3, leading to growth spiral in AlN. The surface defects are attributed to the transformation of amorphous Al2O3 into crystalline structure. The same tendency in the structural quality is also observed by XRD measurements, where the ω‐scan of symmetric (0002) and asymmetric (10true1¯2) reflections increases with ALD‐Al2O3 thickness. Raman analysis and XRD measurements both confirm that AlN epilayers exhibit tensile strain and approach the relaxed state with increasing ALD‐Al2O3 thickness. The high‐quality AlN grown on 1‐nm‐thin ALD‐Al2O3 exhibits the highest tensile strain, effectively circumventing the relaxation through the reduction of threading dislocations.