AbstractCu‐incorporated ordered hexagonal mesoporous silicates (Cu‐MCM‐41) with spheres‐within‐a‐sphere hollow structure have been synthesized using thermoreversible polymer hydrogel methylcellulose (MC) and cationic surfactant as co‐templates, which have been characterized by scanning electron micrograph (SEM), X‐ray diffraction (XRD), transmission electron micrograph (TEM), and N2 adsorption‐desorption isotherms. The obtained results indicate that the morphology of Cu‐incorporated MCM‐41 materials is "spheres‐within‐a‐sphere" hollow structure, which is very similar to that of the alveolus. In benzene hydroxylation with H2O2, the hollow spheres show much higher catalytic activity than particles of Cu‐MCM‐41.