The Bi7-xCexTi4.2Ta0.3W0.5O21 (BTTW-BITT-xCe, x = 0.05, 0.10, 0.15, 0.20) ceramics were studied as potential materials for high-temperature applications. The microstructure, dielectric, piezoelectric and ferroelectric properties of Ce doped BTTW-BITT samples were analyzed in detail. The results indicated that an appropriate amount of Ce ion doping could inhibit the growth of grains, suppress the relaxation peak, reduce high-temperature dielectric losses, and greatly improve the piezoelectric activities. The optimal ceramics was obtained at x = 0.15, which possessed a maximum piezoelectric constant of d(33) = 23.4 pC/N, a high Curie temperature of 713 degrees C, a loss value of 6% at 500 degrees C, and a favorable thermal stability of d(33) = 21.1 pC/N (90% of the initial value) at 500 degrees C. This result indicates that BTTW-BITT-0.15Ce has great potential for applications in the high temperature fields. In addition, XPS results showed that there were two Ce valences states, Ce3+ and Ce4+ present in the BTTW-BITT-xCe ceramics.