In order to obtain dense PbNb 2 O 6 -based piezoelectric ceramics with a single orthorhombic ferroelectric phase, Ba, and excess Ti were doped into PbNb 2 O 6 ceramics with the composition of Pb 0.92 Ba 0.08 Nb 2 O 6 -0.25 wt% TiO 2 via a conventional solid-state reaction method. The ceramics were sintered at 12101-13001C. The effects of sintering temperature on the crystallite structure, microstructure, and dielectric and piezoelectric properties were studied in detail. All ceramics had shown a high relative density (494%) and a single orthorhombic phase. The lattice parameters, grain size, and shape varied with changing sintering temperature. All ceramics exhibited a typical characteristic in ferroelectrics with normal paraelectricferroelectric phase transition at the Curie temperature. With increasing sintering temperature from 12101 to 13001C, the Curie temperature decreased from 5541 to 5231C, while the maximum dielectric constant increased. The change in dielectric properties with changing sintering temperature is associated with a competing effect among internal stress, porosity, and grain size. The ceramic sintered at 12601C possesses an excellent piezoelectric constant (d 33 5 82 pC/N), low mechanical quality factor (Q m 5 20.52), low dielectric loss (tan d 5 0.0062), and high Curie temperature (T c 5 5351C), presenting a high potential to be used in high-temperature applications as piezoelectric transducers.