Three dimensional (3D) printing has been used to fabricate bioceramic scaffolds for treating the tumor-related defects in recent years, but the fabrication process and the introduction of anti-tumor agents are still challenging. In this study, porous free carbon-embedding larnite (larnite/C) scaffolds have been successfully fabricated by 3D printing of the silicone resin loaded with CaCO3 filler and high temperature treatment under an inert atmosphere. The fabricated larnite/C scaffolds had uniform interconnected macropores (ca. 400 μm), and exhibited excellent photothermal effect, which was able to kill human osteosarcoma cells (MNNG/HOS) and inhibit the tumor growth in nude mice. Moreover, the larnite/C scaffolds could stimulate the expression of osteogenesis-related gene (ALP, OCN and Runx-2) in rat bone mesenchymal stem cells (rBMSCs), and also promoted new bone formation in critical-sized rat calvarial defects. Therefore, the combination of 3D printing with polymer-derived ceramics strategy could fabricate multifunctional bioceramic scaffolds, which would be promising for potential application in treating tumor-related bone defects.