To address the need for simultaneous improvements in strength, elasticity, and environmental resilience of rubber materials for flexible electronics, a bioinspired multiscale crosslinking strategy is proposed for systematic performance optimization. Inspired by reversible π–π interactions in transporter protein hinges, we designed a multiscale architecture that integrates a dynamic covalent network with π–π stacking structure, enabling the rubber to exhibit mechanical strength, elasticity retention, and environmental adaptability far exceeding similar studies. Acrylamide is grafted onto styrene–butadiene rubber chains to introduce polar groups. Tris(4-aminophenyl)amine initiates a deamination polycondensation reaction, forming a stable, reversibly tunable covalent network. It exhibits high tensile strength (9.88 MPa) and large elongation at break (992%). Incorporation of 7 wt% graphene forms a conductive network, enhancing conductivity (0.37 S m−1) and strength (14.88 MPa) for flexible sensing. The π−π stacking promotes the movement of delocalized π-electrons in graphene, enabling the triboelectric nanogenerator to possess a high power density (4.2 W m−2) far exceeding similar studies, and to operate stably in complex environments. It enables high-accuracy material recognition (98.58% by machine learning) and real-time human motion monitoring. This work presents a strategy for designing high-performance, self-powered rubber devices for flexible electronics and wearable health monitoring.