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 ~400 μm) and an overall porosity above 70 %, combined with a relative high compressive strength (~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.