By reactively sputtering Zr and Al2O3 targets in a gaseous mixture of Ar and N2, ZrN/AlON nanomultilayers were synthesized to study the crystallization conditions for AlON layers and how they influence the characteristics of multilayers. The composition analysis indicated that some of the oxygen atoms were replaced by nitrogen atoms in Al2O3, leading to the formation of aluminium oxynitride, AlON, during the procedure of the Al2O3 target being sputtered in the gaseous mixture. Further investigations showed that when their thickness was limited to less than 1 nm, amorphous AlON layers were crystallized under the template effects of crystalline ZrN layers, and then coherent interfaces formed as a result. Correspondingly, the multilayers were remarkably strengthened with hardness approaching a maximum of 33 GPa. After the layer thickness of AlON exceeded the critical value of 1 nm, the subsequently deposited AlON grew amorphously and blocked the epitaxial growth of multilayers, accompanied by the decline of hardness. Yet, on the other hand, the integrated hardness of multilayers was not sensitive to the thickness of the ZrN template layers and its value was maintained a bit higher than 30 GPa in a wide range of ZrN layer thickness variations.