Piezoelectric ceramic specimens with the Pb(Mg_1/3Nb_2/3)_0.65Ti_0.35O₃ (PMN-PT) composition are prepared by the solid state reaction method known as the “columbite precursor” method. Moreover, the effects of the Li₂O-Bi₂O₃ additive on the microstructure, crystal structure, and piezoelectric properties of sintered PMN-PT ceramic samples are investigated. The addition of Li₂O-Bi₂O₃ lowers the sintering temperature from 1,200°C to 950°C. Moreover, with the addition of >5 wt.% additive, the crystal structure changes from tetragonal to rhombohedral. Notably, the sample with 3 wt.% additive exhibits excellent piezoelectric properties (d33 = 596 pC/N and Kp = 57%) and a sintered density of 7.92 g/cm³ after sintering at 950°C. In addition, the sample exhibits a curie temperature of 138.6°C at 1 kHz. Finally, the compatibility of the sample with a Cu electrode is examined, because the energy-dispersive X-ray spectroscopy data indicate the absence of interdiffusion between Cu and the ceramic material.