To reduce the toxicity of mesoporous materials in the process of preparation and improve its order, onion-like mesoporous silica was successfully assembled through hydrothermal synthesis, using tetraethoxysilane as silica source, P123 surfactant as template, and environment-friendly span80 as auxiliary agent in aqueous media at different mass ratios (span80/P123 = 10, 15, 20, 25 and 30 %). Multiple characterization technologies such as FT-IR, SEM, TEM and N 2 isothermal adsorption-desorption suggested that the onionlike mesoporous materials could be formed when the mass ratios of span80/P123 = 10, 15, 20, 25 %. When the mass ratio of span80/P123 reached 30 %, the material was with foam morphology. The adsorption experiments showed that all samples exhibited high ability to absorb methylene blue (MB). Our success in synthesizing the onion-like mesoporous materials using environment-friendly agent could provide a new route to the morphology control of mesoporous materials.