New electron doped double perovskite compound (Sr2-xSmx) FeMoO6 (0≤x≤0.25) has been synthesized by solid-state reaction. Crystal structure and magnetic properties of the compounds have been investigated by X-ray powder diffraction (XRD) and magnetic measurements. XRD revealed that all the compounds were of single phase and belonged to a I 4/m lattice. The degree of cationic ordering on the B site was decreased pronouncedly by the electron doping. Different from the results of La- and Nd-doped Sr2FeMoO6, Curie temperature (TC) of (Sr2-xSmx) FeMoO6 decreased first with the doping and then increased beyond x = 0.15, indicating that steric effect was enhanced as the radius of rare-earth ions decreased.