In this study, (1 - x)NaNbO3-xBa(0.6)(Bi0.5K0.5)(0.4)TiO3 (abbreviated as NN-xBBKT, x = 0.05, 0.10, 0.15, and 0.20) lead-free pyroelectric ceramics were synthesized by conventional solid-state reaction method. Moreover, their microstructure, phase structure, dielectric, ferroelectric, piezoelectric, and pyroelectric characteristics were studied systematically. The X-ray diffraction result showed that the phase structure of NN-xBBKT ceramics changed from orthorhombic to tetragonal and finally became pseudocubic symmetry. The ferroelectric-paraelectric phase transition temperature and depolarization temperature shifted to lower temperature with the increase in BBKT content. Furthermore, with increasing BBKT content, piezoelectric coefficient, figures of merit, and pyroelectric coefficient first increased and then decreased. The optimum pyroelectric properties (eg F-d = 0.81 x 10(-5) Pa-1/2, F-v = 1.02 x 10(-2) m(2) C-1, F-i = 1.04 x 10(-10) m V-1, and p = 3.11 x 10(-8) C cm(-2) K-1) were observed in sample composition with x = 0.15. More importantly, the pyroelectric coefficient of ceramic with x = 0.15 also displayed relatively high thermal stability because of high depolarization temperature (similar to 110 degrees C). These parameters demonstrate that the novel Pb-free NaNbO3-based ceramics form an important class of pyroelectric material with broad range of application prospect.