Assemblies of biomaterials onto mechanically stable inorganic structure are advantageous for the practical applications because of the potential to improve the stability and performance of biomaterials in the biocatalytic processes. Among many kinds of inorganic materials, mesoporous materials such as mesoporous silica and mesoporous carbon have attracted special attention owing to their well-defined structures and perfectly controlled pore geometries, which would lead to unique functions such as size selective adsorption of biomaterials. In the first part of this review, adsorption behaviors of proteins, enzymes, vitamins, and amino acids in aqueous solutions onto mesoporous media are systematically explained. Pore geometries (pore diameter and volume) of mesoporous materials are the crucial factors for the size selective adsorption of biomaterials, especially proteins, which often have a size comparable to pore dimension. The studies on the adsorption of biomaterials on the mesoporous carbon reveal that hydrophobic interaction between guest molecules and surface of the mesoporous materials is an important parameter which controls the amount of biomaterials adsorption. Enhanced adsorption of biomaterials was commonly observed at their isoelectric point, where electrostatic repulsion is minimized between the biomaterials. In addition, several functions such as biomolecular separation, reactor function, controlled drug release, and photochemical properties are discussed in the latter sections. Studies on assemblies of biomaterials in mesoporous media are still in initial stage, but the development of appropriately designed mesoporous materials would powerfully promote researches in these fascinating unexplored fields.