A challenge exists for understanding the origin of color for structurally colored, 3-dimensional bioorganic nanostructures, such as the scales of butterflies, beetles, and moths. Complex, hierarchical structures found within such scales create the overall scale appearance. The controlled alteration of color through material deposition and the addition of new optical functionalities to such structures are other areas of scientific interest. This dissertation addresses these challenges with a first-of-its-kind, systematic isolation (deconstruction) of scale component nanostructures, followed by evaluation of optical property/structure correlations. The additive deposition (constructive alteration) of emissive materials to structurally-colored templates complements this deconstructive approach towards understanding the origin of color in butterfly scales. Discoveries made through this work may help advance the bioinspired design of synthetic optical structures and subsequent color control through the addition of multilayered, emissive optical components.