Single phase (1 − x) PbTiO₃ − (x)Bi(Zn_2/3Nb_1/3)O₃ (x = 0.26, 0.28, 0.30, and 0.32) binary piezoceramics were prepared using solid-state reaction technique. Rietveld analysis confirms the tetragonal phase with P4mm space group for all the compositions studied. The lattice parameters and unit cell volume are shown to increase with increasing Bi(Zn_2/3Nb_1/3)O₃ (BZN) substitution in PbTiO₃(PT). The microstructure of the samples exhibit average grain size distribution (< 10 μm). Energy-dispersive X-ray spectroscopy (EDX) and X-ray Fluorescence (XRF) analysis confirmed the chemical composition of the prepared samples. Temperature and frequency-dependent dielectric studies revealed normal ferroelectric behavior in (1 − x)PT − (x)BZN. High remnant polarization and saturation polarization were attained for 0.74PT − 0.26BZN samples. The Curie temperature (T_c), dielectric constant (ε_r), and remnant polarization decrease with increasing BZN substitution. The recoverable energy-storage density (J_reco) of 0.2105 J/cm³ and efficiency (ɳ) of 67% were achieved for 0.74PT–0.26BZN and 0.68PT − 0.32BZN ceramics, respectively. The enhanced piezoelectric coefficient charge d₃₃ − 409 pC/N was observed for 0.74PT – 0.26BZN. This study provides the route for exploring new piezoelectric materials with enhanced electrical properties.