Lateral thinking in biomimetic materials chemistry has permitted chemists to create fascinating structures that mimic the biomaterials optimized by Nature. The integration of organic and inorganic chemistry at multiple length scales gives optimal performance characteristics to biomaterials, such as bone. In a similar fashion, lateral thinking in our lab has enabled us to consolidate the chemistry of inorganic surfactant-templated mesoporous materials with the organic-inorganic hybrid structure of amorphous xerogels. A new class of materials, periodic mesoporous organosilicas (PMOs), has emerged that marries organic and solid-state chemistry in the channels of hexagonally ordered mesoporous materials. Various organic and organometallic groups may be integrated into the framework, creating materials with novel, tunable properties. Surfactant can be solvent-extracted or ion-exchanged to create a high surface area PMO with the framework and the organic group intact. This renders the organic groups accessible for reaction to give a new type of “chemistry of the channels”.