The physicochemical and thermal behavior of mechanochemically activated Al-Fe3O4 mixtures have been studied. The composition and structural changes undergone in the reaction system have been analyzed by DTA and XRD. Experimental evidence indicates that the nature of the products was dependent on the conditions of mechanochemical and thermal treatments. Under adequate experimental conditions, a self-sustained reaction was triggered, with the production of alpha -Fe and alpha -Al2O3 BY varying the treatment parameters, it was possible, through an alternative reaction path, to obtain different products which show interesting properties in their application as functional materials.