The phase transition and pyroelectric behavior of NayBizTi1−xO3(1−x)–xBaTiO3 (x=0.06–0.08, z/y≧1) ceramics were investigated as functions of temperature and electric field. A dominant antiferroelectric (AFE) ground state is proposed for NayBizTi1−xO3(1−x)–xBaTiO3 (x=0.06–0.08, z/y≧1) ceramics at room temperature (RT). The stability of the induced ferroelectric (FE) phase is closely related to the molar ratio of Na+ and Bi3+. The temperature of the FE to AFE phase transition for the poled samples can be adjusted to RT through a modulation of the molar ratio of Na+ and Bi3+. Pyroelectric current peaks were detected at the FE–AFE transition temperature. Huge pyroelectric coefficients of 905 × 10−8, 3270 × 10−8, and 140 × 10−8°C·(cm2·K)−1 were obtained at phase transition temperatures of 83°, 64°, and 34°C, respectively.