MnO2-modified Pb0.9625Sm0.025(Mg1/3Nb2/3)0.71Ti0.29O3 ceramics were prepared via a solid-state reaction approach. Results of detailed characterizations revealed that the addition of MnO2 has influence on the grain size, and all samples exhibit a pure perovskite structure. As the content of manganese increases, the volume of tetragonal phase increases. The ceramics with 1.5 mol.% MnO2 show a high electro-strain of 0.151% at 2 kV/mm. Therefore, this study provides a new insight into the role of MnO2 addition in tailoring the electrical properties of the Sm-PMN-PT ceramics by acceptor doping.