Perovskite type-materials LaCo((1-x))FexO3 Were prepared from their component oxides using mechanosynthesis, a new method of preparation designated as reactive grinding. When grinding additives are used, the perovskites generated via this process are of unprecedently high specific surface area (> 100 m(2)/g) and their surface chemical properties are of particular interest. The perovskite surface shows a large concentration of surface OH's (due to the low grinding temperature) which upon calcination leads to reformation of the materials lattice. The presence of oxygen during calcination initiates a competitive process, which stabilizes sites with an excess of electronic charge, yielding reduced Co sites upon oxygen desorption (Co2+) At high calcination temperature (> 673 K), TPD studies show the release of beta -oxygen originating from the bulk. In this work, the catalytic properties in the n-hexane oxidation reaction of five nanocrystalline LaCo(1-x)FexO3 perovskites prepared by this method are studied. The low preparation temperature allows to stabilize high surface area (SSA) materials and the adequate control of the calcination conditions allows to tailor the surface properties of these materials. Through a kinetic study of the total oxidation of n-hexane by oxygen, the fine control of the nature and the concentration of the various sites active in oxido-reduction catalysis is demonstrated. Furthermore, the roles of two oxygen species O-2(-) and O- respectively associated with alpha and beta oxygens are discussed.