In this report, we investigate ferroic properties of Nb5+ and Ce4+ co-doped bZr0.95Ti0.05O3 (PZT95/5) ceramics, prepared via conventional solid state reaction route. Room temperature X-ray diffraction pattern suggests that synthesized samples crystallize with rhombohedral crystal symmetry (space group—R3c), equivalent to Zr rich PZT materials. Dielectric constant (er) exhibits anomaly in the vicinity of transition temperature. To unveil, the effect of co-doping on nature of evolved phase, we follow diffusion coefficient, $$\gamma$$ , obtained from modified Curie-Wiess law. Value of $$\gamma$$ is found to be ~ 1.24 and ~ 1.20 for 2% and 3% Ce4+ doped material, respectively, and $$\gamma >1$$ for diffused type ferroelectric (FE) systems. Saturated P-E loop profile evidences that co-doping of Nb5+ and Ce4+ causes strong enhancement in technologically appealing ferroic properties, e.g., spontaneous polarization, remnant polarization and breakdown strength. Such advances in ferroic properties are highly appreciated in field of various ferroelectric-based technology.