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This article studies the microstructure and piezoelectric properties of low sintering temperature lead-free ceramics 0.52(Ba0.7Ca0.3)TiO3−0.48Ba(Zr0.2Ti0.8)O30.52(Ba0.7Ca0.3)TiO3−0.48Ba(Zr0.2Ti0.8)O3-doped with ZnO nanoparticles (noted as 0.48BZT-y, y is content of ZnO in wt%, y =0.00, 0.05, 0.10, 0.15, 0.20 and 0.25). The obtained results of Raman scattering and dielectric measurements have confirmed that Zn2+Zn2+ has occupied B site, to cause a deformation in the ABO₃-type lattice of the 0.48BZT-y compounds. The 0.15 wt% ZnO-doped ceramic sintered at 1350∘∘C exhibited excellent piezoelectric parameters: d33=420pC/Nd33=420pC/N, d31=−174pC/Nd31=−174pC/N, kp=0.483kp=0.483, kt=0.423kt=0.423 and k33=0.571k33=0.571. The obtained results indicate that the high-quality lead-free BZT–BCT ceramic could be successfully synthesized at a low sintering temperature of 1350∘∘C by doping an appropriated amount of ZnO.