Electrochemical formation of aluminum nitride was investigated in molten LiCl–KCl–Li 3 N systems at 723K. When Al was anodically polarized at 1.0V (versus Li + /Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1–5μm of diameter) of wurtzite structure.