Depending on milling conditions (air or vacuum) for the same milling time, a different level of decomposition and structure disorder in BaFe12O19 ferrite powders can be obtained by ball milling. Air-milled material has a tendency to form a gas-saturated disordered structure (superoxide) and to transform into simple oxides (reduction process through oxygen-saturated disordered phase) as opposed to the vacuum-milled powder where a highly disordered phase occurs. Both powders have a different morphology (particle size and distribution). Annealing processes produce crystalline barium ferrite phase with interesting magnetic properties, but in the present paper only structural transformations are analysed. Scanning electron microscopy, X-ray diffraction and thermal analysis techniques were applied to study the effects of heat treatment (10 h at 773 or 1273 K) in disordered BaFe12O19 ferrite powders prepared by 1000 h ball milling in air and vacuum.