The double perovskite Sr(2)FeMoO(6) has been prepared in polycrystalline form by high-pressure methods, starting from a precursor developed via a citrate technique, containing an elevated degree of anti-site disordering. The application of high external pressure (2 GPa) to Sr(2)FeMoO(6) promotes the long distance Fe/Mo cationic order, due to the smaller lattice volume of the ordered sample. Both the disordered perovskite obtained at ambient pressure and the sample synthesized under high-pressure methods have been characterized by means of x-ray diffraction, neutron powder diffraction and magnetic measurements. The magnetic properties of the two oxides have been compared; the specimen prepared under high pressure not only presents an improved cationic ordering, but also displays a superior saturation magnetization and a sharpener ferromagnetic transition at a significantly high temperature of 430 K.