Colossal dielectric perovskites enable Coulombic interfacial β-phase stabilization

Soft piezoelectric polymers hold promise for the advancement of flexible wearable sensors offering self-powered precise monitoring capability. However, their long-term stability of performance is often constrained by modest crystallinity and insufficient dipole alignment. To conquer this, we fabricated a polymer-inorganic hybrid via Coulombic interfacial field anchoring. Using the colossal permittivity perovskite (CaCu 3 Ti 4 O 12 ) as a dielectric template intensifies interfacial field under electrospinning, driving fluoropolymer chain into all-trans conformation and stabilize ferroelectric switching. This electrostatic coupling elevates the β-phase content and remanent polarization, delivering an exceptional 700% gain in piezoelectric response relative to pure poly(vinylidene fluoride). Leveraging the stable electromechanical response and mechanical endurance, the nonwoven fabric were implemented into a helmet liner, which maps impact location and severity in real time, and a three-dimensional–structured insole enabling early-stage fall detection. This works demonstrates a Coulombic interaction–driven intermolecular anchoring approach to produce high-performance organic-inorganic piezoelectric nanocomposites, expanding the capabilities of electromechanical smart monitoring.