Hierarchically 3D porous mesoporous bioactive glasses (MBGs) scaffolds with four different chemical compositions have been successfully prepared by a combination of polyurethane sponge and non-ionic block copolymer EO₂₀PO₇₀EO₂₀ (P123) surfactant as co-templates and evaporation-induced self-assembly process. The structure and morphology of these scaffolds were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N₂ adsorption-desorption technique. All scaffolds have the interconnected macroporous network (pore diameter of 200-400 μm) and mesoporous walls (mesopore size of 4.9 nm). Furthermore, the mesostructure and textural properties are close to each other. The in vitro bioactivity of these MBGs scaffolds is dependent on the chemical composition. The introduction of Ca and P into the network facilitates the formation of hydroxylcarbonate apatite (HCA) layer on the surfaces of scaffolds. Cell cultures for 1, 3 and 7 days indicated that primary human bone-derived cells (HBDC) on the scaffolds of MBGS 80S15C (S and C represents SiO₂ and CaO; 80 and 15 is the molar ratio of SiO₂ and CaO in percentage × 100, respectively) present a better attachment than those on the scaffolds of MBGS 70S25C, MBGS 90S5C and MBGS 100S.