This present study aims to fabricate and characterize a series of new complex-structured ceramics with formula (1-x)Pb(Zr0.52Ti0.48)O3-xBi3.99Ti2. 97Nb0.03O12 or (1-x)PZT -xBNbT (when x 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) using a solid-state mixed oxide method and sintered at temperatures in between 950-1050°C for 4 h with a heating/cooling rate of 5°Cmin-1. It was found that the optimum sintering temperature was 1000°C. The result of phase analysis using X-ray diffraction (XRD) indicated the existence of PZT-as well as BNbT-based solid solutions with corresponding lattice distortion. The solubility limit of ∼50 wt% PZT in BNbT was observed for BNbT-rich phase. Scanning electron micrographs of ceramic surfaces showed a plate-like structure in BNbT-rich phase which started to dominate at 0.5PZT-0.5BNbT composition. The microstructural evolution in this system was found to be in agreement with X-ray diffraction analysis. © Published under licence by IOP Publishing Ltd.