In this study, a new lead-free ceramic system of (1–x)Bi0.5Na0.5TiO3–0.065BaTiO3–xSrZrO3 BNBT–SZ100x (with x = 0–0.10) was prepared by a conventional solid-state reaction method and its structural and electrical properties were studied. XRD analysis revealed the formation of pure perovskite phase for all ceramics. The temperature dependence of the dielectric curves showed that the maximum dielectric constant temperature (Tm) shifted towards lower temperatures and the curves become more diffuse with increasing amount of SZ addition. The ferroelectric curves indicated a disruption of ferroelectric order upon SZ addition into BNBT ceramics. A maximum value of remnant polarization (30 µC cm−2), piezoelectric constant (197 pC N−1) and electromechanical coupling coefficient (29.4%) was observed for SZ1 ceramics.