Doping effects of CuO on the sintering behavior and electrical properties of 0.94(Bi0.5Na0.5)TiO₃–0.06(BaTiO3)–xCuO (BNT–BT6–xCu) lead-free piezoceramic obtained by the conventional solid-state reaction method were investigated. Regarding the undoped system, it is already known that it presents the best densification values when it is sintered at 1150∘C, however, the doped system was sintered at 1150∘C, 1100∘C, 1050∘C, 1025∘C, and 975∘C to determine the effect of Cu on the densification process. Therefore, it was obtained that the CuO-doped samples sintered at 1050∘C presented the highest density values and therefore were the ones chosen to perform the characterization tests together with the undoped system. The samples were characterized using X-ray diffraction (XRD), Raman microspectroscopy, and scanning electron microscopy (SEM) analysis, whereas the ferroelectric and dielectric properties were evaluated by means of ferroelectric hysteresis loops and impedance spectroscopy studies. As a result, the addition of CuO allowed an improvement in sinterability and densification, with the subsequent grain growth, and the improvement of the piezoelectric coefficient (d33).Doping effects of CuO on the sintering behavior and electrical properties of 0.94(Bi0.5Na0.5)TiO₃–0.06(BaTiO3)–xCuO (BNT–BT6–xCu) lead-free piezoceramic obtained by the conventional solid-state reaction method were investigated. Regarding the undoped system, it is already known that it presents the best densification values when it is sintered at 1150∘C, however, the doped system was sintered at 1150∘C, 1100∘C, 1050∘C, 1025∘C, and 975∘C to determine the effect of Cu on the densification process. Therefore, it was obtained that the CuO-doped samples sintered at 1050∘C presented the highest density values and therefore were the ones chosen to perform the characterization tests together with the undoped system. The samples were characterized using X-ray diffraction (XRD), Raman microspectroscopy, and scanning electron microscopy (SEM) analysis, whereas the ferroelectric and dielectric properties were evaluated by means of ferroelectric hysteresis loops and impedance spectroscopy studies. As a result, the addition of CuO allowed an improvement in sinterability and densification, with the subsequent grain growth, and the improvement of the piezoelectric coefficient (d33).