Abstract: Methods of controlling orientational ordering in self-assembled materials are described. These methods include controlling the nucleation rate and growth of block-copolymer-templated silica domains to yield macroscopically aligned mesostructured materials, and forming patterned mesostructured films or monoliths with control over the direction of alignment of a hexagonally-packed, block-copolymer-directed mesostructure across macroscopic lengths scales are described. Self-assembled materials with controlled orientational ordering are described, including those that contain a surfactant or block-copolymer species, and materials that include an organic (e.g., resin) or inorganic (e.g., silica or titania) network-forming component.