Mesoporous materials have great application value in the fields of supercapacitors, [1] catalyst, [2] optical materials, [3] chromatographic separation, and drug delivery. [4,5] Most of mesoporous materials are prepared by self-assembly of various ionic and block copolymer surfactants, [6,7] which can form a variety of selfassembled structures, [8] from spherical or rod-shaped micelles,The interactions of ions and molecules with material surface are highly dependent on the surface properties of the material. Therefore, the distribution of ions or molecules near the material surface may be affected by the surface properties. This phenomenon can be significant enough for controlling the structure of a material synthesized in the sub-micrometer scale confinement space of a template. This work confirms that inverse opals are perfect templates for offering confinement space, while their different surface properties can strongly affect ion and block copolymer distribution in the confinement space. This surface effect principle can be used for the controlled synthesis of colloids with complex composition. As an example, four kinds of mesoporous magnetic bioactive glass colloids with ordered mesopores, coreshell structure, open surface pores, or disordered mesopores are prepared by using polystyrene and carbon inverse opal templates. This work reveals that inverse opal templates possess great advantage in controlled synthesizing colloidal structures due to their surface effect on ions and molecules and confinement space.to hexagonal packed liquid crystal phase, 3D bicontinuous phase, [9,10] and 2D layered phase. [11,12] Many methods have been used to prepare mesoporous particles of different structures in the past 30 years. For example, hollow mesoporous silica spheres were prepared by emulsion chemistry [13] and template synthesis methods, [14] and solid mesoporous microspheres were prepared by an aerosol means. [15] Micrometer-and sub-micrometer-size mesoporous silica microspheres were prepared with well-controlled uniform size. [16] Core-shell silica microspheres with solid core and mesoporous shell were prepared by using silica microspheres as a template. [17] Although many achievements have been obtained, in recent years, the development of theoretical and experimental research on mesoporous materials is relatively slow.Mesoporous bioactive glasses (MBG) are promising materials for drug carrier and tissue engineering. [18] They have better biodegradable and biocompatible properties than pure mesoporous silica due to additional ions in silica network; they are more robust and have higher specific surface area and pore volume than polymer and peptide drug carriers. Many metal ions are doped into BGs to expand their application. Boron-doped Bioglass 45S5 (45.0SiO 2 ·24.5Na 2 O·24.5CaO·6.0P 2 O 5 , wt%) has better biological activity due to its faster dissolution than silicate glasses and almost complete conversion to hydroxyapatite (HA). [19] Adding Zn 2+ , Ag + , or Cu 2+ can endow BG with well antimicrobial activity....