Bismuth sodium titanate (BNT) piezoelectric ceramic coatings with dense morphology and single perovskite phase were fabricated by thermal spray process. The melting and crystallization behaviors of BNT near congruent composition and the effect of excess Bi composition were investigated by analyzing the heating-melting-cooling cycle for the application in thermal spray process. Crystal structure and morphology of the thermal sprayed BNT coatings were examined, and their electrical and electromechanical properties were tested. An effective piezoelectric coefficient d(33) of 50 pm/V was obtained under substrate clamping, measured with laser scanning method. The findings have shed light on the design of appropriate compositions for achieving high quality lead-free piezoelectric ceramic coatings by the scalable thermal spray process.