Nanocomposites offer the theoretical potential to achieve mechanical properties surpassing those of conventional (micro-scale) composites. The underlying reasons for the high potential of nanocomposites include the uniquely high mechanical attributes of nano-scale reinforcement, effective control of defect size and growth by nano-spaced interfaces, and interactions between the polymer matrix and the large surface areas of nanomaterials. Attempts to produce nanocomposites via conventional processing techniques have encountered challenges associated with thorough dispersion and effective interfacial interactions of nano-scale reinforcement with the polymer matrix. In order to address these challenges, materials were processed into polymer nanocomposites via electrostatically driven layer-by-layer self-assembly. Electrostatically dispersed nanomaterials and oppositely charged polyelectrolytes were sequentially built upon a substrate (cellular scaffold). The self-assembled nanocomposites, after complementary cross-linking, provided a unique balance of strength and ductility, which surpassed those of conventional (micro-scale) composites. Self-assembly was found to be an effective approach to producing nanocomposites embodying uniformly dispersed nanomaterials with controlled interfacial interactions. This approach is highly versatile and enables introduction of diverse nanomaterials into polymer nanocomposites. The work reported herein evaluated introduction of diverse categories of nanomaterials incorporating nanoparticles, nanosheets, nanotubes, and nanofibers. This investigation also evaluated the potential for a biomimetic approach to processing of light-weight structural systems by self-assembly of polymer nanocomposites onto cellular scaffolds.