A low-cost, efficient method of preparing hierarchically ordered structures by filling a minimold with a microsphere-containing latex suspension, forming an close-packed array of microspheres within the minimold and filling void space in the array with a self-assembling mixture of hydrolyzed inorganic species and amphiphilic block copolymers. A macroporous and mesoporous material can be produced by subsequent thermal removal of the microspheres and copolymers.