In this paper, the structural and ferroelectric properties of PbTiO3-modified 0.6Ba(Ti0.8Zr0.2)O3-0.4(Ba0.7Ca0.3)TiO3 ceramics are reported. The nonlinear electric polarization is observed at room temperature in 0.6Ba(Ti0.8Zr0.2)O3-0.4(Ba0.7Ca0.3)TiO3 and remained after the introduction of PbTiO3. With increasing the PbTiO3 concentration to 7 mol.%, high electrical remanent polarization of 13.11 µC/cm2 is achieved. The large strain and Smax/Emax values were also obtained in PbTiO3-modified compounds, where the highest piezoelectric coefficient values were estimated at around 642 pm/V for 3 mol.% PbTiO3-addition into 0.6Ba(Ti0.8Zr0.2)O3-0.4(Ba0.7Ca0.3)TiO3 compounds. We expected that the ceramics prepared in our study might be a suitable candidate for applications in electronic devices.