There are provided processes for decomposing AlCl 3 •6H 2 O into γ-Al 2 O 3 that comprise heating the AlCl 3 •6H 2 O at a temperature of about 600°C to about 800°C in the presence of steam and optionally at least one gas (for example chosen from air, argon, nitrogen, carbon dioxide, hydrogen and hydrochloric acid), under conditions suitable to obtain the γ-Al 2 O 3 . For example, the γ-Al 2 O 3 obtained can be suitable for use in an aluminum smelting process or optionally for processes for treating the γ-Al 2 O 3 to obtain high purity alumina, fused alumina, transition alumina, tabular alumina, calcined alumina, ultra-pure alumina or specialty alumina.