Lead-free (1-x)Sr_0.1Bi_0.45Na_0.45TiO₃-xBi_0.5Li_0.5TiO₃ (x = 0-0.4) ceramics were successfully prepared by a solid-state reaction technique. The effects of amount of Bi_0.5Li_0.5TiO₃ on structure and electrical properties were examined. The X-ray diffraction (XRD) analysis revealed that all the investigated specimens have a perovskite structure. An obvious change in microstructure with the increase of Bi_0.5Li_0.5TiO₃ concentration was observed. This study demonstrated that relaxor could be stabilized in Sr_0.1Bi_0.45Na_0.45TiO₃ based ceramics by lowering the tolerance factor and electronegativity difference. Besides, a dielectric anomaly related to thermal evolution of crystallographic symmetry was emerged at the depolarization temperature. Upon incorporation of 26 mol% Bi_0.5Li_0.5TiO₃, the specimens were able to withstand an electric field intensity of 106.9 kV/cm with an energy density of 0.88 J/cm³ and an energy efficiency of 65%.