Piezoelectric ceramics are important materials in electronic components, and their individualized and complex fabrication is important to improve the performance of piezoelectric functional devices. However, due to the high brittleness and hardness of ceramics, traditional molding processes face greater challenges in preparing complex structures. Additive manufacturing, based on the principle of layer-by-layer superposition, can theoretically prepare arbitrary complex structures, providing a new solution for the preparation of complex components of piezoelectric ceramics. In this paper, a lead zirconate titanate (PZT) piezoelectric ceramic skeleton with complex structure was successfully prepared using stereolithography (SLA) additive manufacturing process, and the effect of slurry solid content on the rheological properties of PZT ceramic slurry, the microscopic morphology, the relative density, and the electrical properties of PZT ceramic sintered body was investigated. The results show that the increase of ceramic solid content contributes to the grain growth at high temperature and the densification of billet, but at the same time increases the apparent viscosity of slurry and reduces the curing performance of slurry, which is not conducive to the preparation of PZT with complex structure. In this study, PZT-based ceramic sintered bodies with a relative density of 98.26% and a piezoelectric constant d33 of 341 pC/N are prepared, which provides a reference for the additive manufacturing of high-performance piezoelectric ceramics and their composites.