We carried out AlN synthesis using Li‐Al‐N solvent. In the present work, Al and Li3N were used as source materials. In this paper, we discuss the variation in phase stability of the products with change in Li‐Al‐N composition, i.e., Al/Li3N molar ratio. The results suggest that LiAlO2 extra phase was formed in the products under an Al‐rich synthesis condition. The oxide formation seems to be caused by oxidation of the nitrogen source. That is, some of the Li3N reacted with H2O in the ambient and to be LiOH, though preparation of the source materials was performed in a glove‐box. On the other hand, scanning electron microscopy (SEM) images indicate the possibility of reducing nucleation sites and increasing grain size by optimizing the Al/Li3N molar ratio. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)