(Bi0.5Na0.5)TiO3–BiAlO3 lead‐free materials exhibit excellent ferroelectric properties, but its depolarization temperature is relatively low which is the major obstacle limiting the material's practical application. In this study, the effects of Manganese (Mn) modification on the microstructure, ferroelectric properties and depolarization behavior of 0.96(Bi0.5Na0.5)(Ti1−xMnx)O3–0.04BiAlO3 ceramics were investigated. It was found that the average grain size was enlarged and ferroelectric properties were enhanced with small Mn addition, meanwhile the tangent loss decreased. The remnant polarization (Pr) of the samples reached an optimal value (~41 μC/cm2) as Mn content increased up to 0.7 mol%, whereas further addition resulted in the decrease in Pr. Moreover, appropriate Mn addition (x=0.7%) can improve the depolarization temperature from 140°C to 161°C determined from thermally stimulated depolarization currents measurement.