BaZrO3 doped (Na0.52K0.48)(Nb0.95Sb0.05)O3 ceramics were prepared using solid state route. The optimization of processing parameters like calcination temperature (800 °C), sintering temperature (1140 °C) and poling parameters (3 kV/mm at 120 °C/60 min) was carried out on base composition. Optimized parameters yielded a piezoelectric charge coefficient of 171 pC/N in composition having 4 mol% BaZrO3. Low temperature dielectric measurements and high temperature X-ray diffraction studies, along with structural refinement using Rietveld method were performed to ascertain the new found phenomenon. A castling-like phenomenon was observed in (1-x)(Na0.52K0.48)(Nb0.95Sb0.05)O3 – xBaZO3 (0.00 ≤ x ≤ 0.08) ceramics, where two phases interchanged their position. Also, BaZrO3 led to negative ageing behavior in these ceramics. Doping of BaZrO3 improved the electrical fatigue behavior and degraded the ferroelectric and thermal stability of ceramics.