We utilize nanoconfinements to program how polymers entangle and disentangle as chain clusters to engineer pseudo bonds with tunable strength, multivalency, and directionality. When amorphous polymers are grafted to nanoparticles that are one magnitude larger in size than individual polymer, programming grafted chain conformations can “synthesize” high performance nanocomposites with moduli of ~25GPa and a circular lifecycle without forming and/or breaking chemical bonds. These nanocomposites dissipate external stresses by disentangling and stretching grafted polymers up to ~98% of their contour length, analogous to that of folded proteins; use both polymers and nanoparticles for load bearing; and exhibit a non-linear dependence on composition throughout the microscopic, nanoscopic and single particle levels.