Silicate bioceramic scaffolds are of great interest in bone tissue engineering, but the fabrication of silicate bioceramic scaffolds with complex geometries is still challenging. In this study, three-dimensional (3D) porous β-Ca2SiO4 scaffolds have been successfully fabricated from preceramic resin loaded with CaCO3 active filler by 3D printing. The fabricated β-Ca2SiO4 scaffolds had uniform interconnected macropores (ca. 400 μm), high porosity (>78%), enhanced mechanical strength (ca. 5.2 MPa), and excellent apatite mineralization ability. Importantly, the results showed that the increase of sintering temperature significantly enhanced the compressive strength and the scaffolds sintered at higher sintering temperature stimulated the adhesion, proliferation, alkaline phosphatase activity, and osteogenic-related gene expression of rat bone mesenchymal stem cells. Therefore, the 3D printed β-Ca2SiO4 scaffolds derived from preceramic resin and CaCO3 active fillers would be promising candidates for bone tissue engineering.