The feasibility of fabricating electrochemical cells from nanostructured materials around an inverse opal electrode foundation whose design may be adaptable to battery, capacitor or sensor applications, was examined. Templating with colloidal crystals, arrays of close-packed polymer or silica spheres is a general method of forming three-dimensionally ordered macroporous (3DOM) materials or inverse opals composed of metals, oxides, polymers, and other compositions. A method has been developed to achieve the requirements by combining colloidal crystal templating with electrochemical thin-film growth and soft-gel chemistry. 3DOM carbon monoliths were synthesized and affixed to nickel mesh current-collector strips. The results show that it is possible to assemble the necessary solid-state components in a 3D interpenetrating design using a combination of colloidal crystal templating, electropolymerization (EP), and sol-gel chemistry.