Abstract Single phase PLZT (7/65/35) ceramics doped with Cr2O3 [0,0.05, 0.08, 0.18, 0.30 0.50, 0.75 and 1.0 wt%] were synthesized by high temperature solid-state reaction technique accompanied by hot pressing. XRD studies revealed that the chromium doping reduces the lattice parameter of PLZT (7/65/35) without changing its crystal structure. A relaxor like behavior with decrease in temperature of dielectric constant maxima (Tm) was observed with increase in chromium content. A sharp rise in the conductive losses were observed for higher chromium (≥0.08 wt%) contents. The room temperature dielectric constant (e′RT) and electromechanical coupling coefficient (k31) showed maxima value for 0.08 wt% Cr2O3 doped PLZT (7/65/35) ceramic. The results were interpreted on the basis of multiple valence nature of chromium.