Preparation methods (ceramic and sol–gel methods) using reducing conditions were optimized for the formation of phase pure double perovskites of Sr₂FeMo_(1−x)W_xO₆ (0 ≤ x ≤ 1) showing enhanced homogeneity and cation ordering for investigating magnetic properties. X-ray diffraction (XRD) revealed a structural transition from tetragonal to monoclinic as W replaces Mo (x = 0.5–0.6). The SQUID magnetometry confirmed a ferrimagnetic ground state for Sr₂FeMoO₆ whereas Sr₂FeWO₆ shows an antiferromagnetic state. Current results demonstrate that improved preparation methods can enhance the saturation magnetization.