The 3 mol% Nb2O5 doped Pb(Zr0.52Ti0.48)O3 with addition of 1-3 mol% Cr2O3 prepared via the solid-state reaction technique have been investigated. The XRD shows that a sample is primarily in both tetragonal and rhombohedral phases coexist and the amount of rhombohedral phase decreases that is due to the donor (Nb) dopant reduces the number of oxygen vacancies and leads to a lower amount of rhombohedral phase. The maximum dielectric constant tend to decrease with increasing Cr doping concentration from 0.1 to 1 mol%. Further increase in Cr concentration, the maximum dielectric constant increase dramatically. The hysteresis loop measurements, the electrical coercivity and the remnant polarization do not show a systematic trend at low concentration of Cr doping. It is possibly due to the partial solubility of Cr doping. The observations clearly indicate the hardening behavior at higher concentration because of more solubility of Cr.