Here we report the synthesis of mesoporous metal oxide materials with various compositions by assembly of spherical polymeric micelles consisting of triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-PVP-b-PEO) with three chemically distinct units. The PVP block interacts strongly with the inorganic precursors for the target compositions. The hydrophobic PS block is kinetically frozen in the precursor solutions, enabling the spherical micelles to remain in a stable form. The frozen PS cores serve as templates for preparing robust mesoporous materials. The PEO corona helps the micelles to stay well dispersed in the precursor solutions, which plays a key role in the orderly arrangement of the micelles during solvent evaporation. This approach is based on assembly of the stable micelles using a simple, highly reproducible method and is widely applicable toward numerous compositions that are difficult for the formation of mesoporous structures.