Mesoporous bioactive glass (MBG) nanoparticles prepared by sol-gel method have attracted much attention in various biomedical applications due to their customizable microstructures and chemical composition. Notably, dendritic mesoporous bioactive glass (DMBG) nanoparticles with unique open three-dimensional dendritic structures are promising biomaterials for bone regeneration. Cerium, a rare-earth element, when applied to biomaterials can transform its oxidation state between Ce3+ and Ce4+, thus regulating the reactive oxygen species level in the body, exhibiting antioxidant activities and further facilitating osteogenesis. Cerium doped bioactive glasses have been evidenced to present antioxidant, antibacterial, osteogenic and angiogenic properties. In this work, we prepared dendritic mesoporous silica (DMS) nanoparticles via sol-gel approach by using dual templates at ultralow concentration in an organic solvent free system. By using impregnation strategy, Ca and Ce can be easily incorporated into silica network resulting DMBG and Ce-DMBG nanoparticles, guaranteeing the microstructural integrity and dimensional stability. Physicochemical characterizations were performed on the nanoparticles. Both synthesized DMBG and Ce-DMBG serial nanoparticles were amorphous, negatively charged, with hydrodynamic size of around 200 nm in aqueous solution. After soaking in SBF 7 days, hydroxyapatite was verified on both DMBG and Ce-DMBG nanoparticles by FTIR, XRD, and SEM-EDS analyses, indicating their great prospect for bone regeneration application.