Asymmetric polymeric materials can be formed by either top-down or bottom-up methods. Bottom-up methods involve assembling the atoms and molecules to form small nanostructures by carefully controlled synthesis, which results in a reduction of some of the top-down limitations. In this dissertation, thermal, tribological and antireflective properties of polymeric materials have been enhanced by introducing structural asymmetry. The overall performance of commercial polymeric coatings, e.g. epoxy and polyvinyl chloride, has been improved by conducting the blending methods, specifically, chemical modification (α,ω-dihydroxydimethyl(methyl-vinyl)oligoorganosiloxane), cross-linking (triallyl isocyanurate), and antioxidant (tris(nonylphenyl) phosphite) incorporation. The nonequilibrium polymeric structures (moth-eye and square array) have been developed for the ultrahigh molecular weight block copolymers via the short-term solvent vapor annealing self-assembly. The large domain size of the moth eye structure allows for improvement of the light transmittance particularly in the visible and near infrared ranges, while the square arrangement of the block copolymer opens the possibility of magnetic data storage application by the large magnetic nanoparticles' embedment or masking of the superconductors.