In contrast to the substitution of exotic elements such as Mn, Cu for Fe or W for Mo in Sr 2 FeMoO 6 , the degree of ordering of Fe and Mo in Sr 2 Fe x Mo 2−x O 6 shows a maximum at x C =0.95 and decreases as x deviates from x C . Saturation magnetization depends upon composition in a similar way. It is shown that the entropy due to antisite defects or substitutional disorder can stabilize the double perovskite structure. It is proposed that the stability of the double perovskite structure of Sr 2 Fe x Mo 2−x O 6 is essentially determined by the combined contribution to free energy of configuration entropy and differences in ionic charge and in ionic radius. A plausible charge distribution of Fe and Mo cations in Sr 2 Fe x Mo 2−x O 6 is proposed to elucidate the observed composition-dependence of magnetization.