In the study, we developed hierarchical composite scaffolds by 3D printing technique with mesoporous CaSiO3 containing controlled amounts of Ce substitution in Ca-Si system. The scaffolds were porous with 3D interconnected large pores (size similar to 400 mu m) and an overall porosity above 70 %, combined with a relative high compressive strength (similar to 7 MPa). These properties are essential for enhancing bone ingrowth in tissue engineering. The in vitro biological properties of apatite formation, cell proliferation, and differentiation were characterized on CeO2-MCS scaffolds and MCS scaffolds. Results indicated that CeO2-MCS scaffolds induced similar apatite deposition and cell attachment of human bone marrow stromal cells. In addition, CeO2-MCS scaffolds enhanced expression of alkaline phosphatase, osteogenesis genes (bone morphogenetic protein-2, collagen type I), and angiogenesis gene markers (fibroblast growth factor and vascular endothelial growth factor), compared to that for MCS scaffolds. Therefore, the 3D-printed CeO2-MCS scaffolds showed the potential of enhanced osteogenic activity.