In this work, we have studied a new lead-free ceramic of (1−y)Bi1−x
BiScO3 (0.05≤x≤0.15 and 0.05≤y≤0.15) prepared by a conventional solid-state method, and the influences of Nd and Sc content on their phase structure and electrical properties were investigated in detail. The ceramics with 0.05≤x≤0.10 and 0.05≤y≤0.15 belong to an R3c phase, and the rhombohedral-like and orthorhombic multiphase coexistence is established in the composition range of 0.125≤x≤0.15 and y=0. The electrical properties of the ceramics can be enhanced by modifying x and y values. The highest piezoelectric coefficient (d
33~51 pC/N) is obtained in the ceramics with x=0.075 and y=0.125, which is superior to that of a pure BiFeO3 ceramic. In addition, a lowest dielectric loss (tan δ~0.095%, f=100 kHz) is shown in the ceramics with x=0.15 and y=0 due to the involvement of low defect concentrations, and the improved thermal stability of piezoelectricity at 20–600°C is possessed in the ceramics. We believe that the ceramics can play a meaningful role in the high-temperature lead-free piezoelectric applications.