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Inspired by spider silk, we have designed a series of polymer-peptide polyurethane/ureas to explore the hierarchical arrangement critical to energy absorption and mechanical enhancement. We have developed chain-extended and non-chain extended peptide-polyurea hybrids with tunable secondary structure, modulating extensibility, toughness, and stiffness. The sheet-dominant hybrid materials were typically tougher and more elastic due to intermolecular H-bonding, while the helical-prevalent systems generally exhibited higher modulus. We have also explored the impact of a molecular design strategy that overlays a covalent and physically crosslinked architecture in these hybrids, demonstrating that physical constraints in the network hybrids influences hydrogen bonding and morphology. More recently, tailored physical associations within the soft and hard phases were engineered as a function of peptide content, leading to a rheological response dictated by block ordering and highlighting their potential as structural and injectable hydrogels. New efforts in silk composites that exhibit shape memory behavior, and 'green' pathways for silk-inspired materials are of current focus. These structural features have enabled new thrusts in injectable gels and responsive actuators.