The preparation of natural rubber (NR)-silica (SiO2) elastomeric composites with excellent mechanical properties along with better self-healing ability remains a key challenge. Inspired by the energy dissipation and repairability of sacrificial bonds in biomaterials, a strategy for combining covalent and noncovalent sacrificial networks is engineered to construct a dual hybrid network. Here, the approach used to fabricate the composites was self-assembly of NR, bearing proteins and phospholipids on its outer bioshell, with SiO2 via metal-ion-mediated heteroaggregation effected by reversible electrostatic and H-bonds. Further, covalent cross-links were incorporated by a silane coupling agent, bis [3-(triethoxysilyl) propyl] tetrasulfide. The intrinsic self-healing ability of the composite at the molecular level was studied by broadband dielectric spectroscopy that unraveled the mechanism of the healing process. The synergistic effect between the molecular interdiffusion of the cross-linked NR chains and the electrostatic and H-bonding interactions imparted an exceptional self-healing characteristic to the liquid-liquid-mixing-prepared NR-SiO2 composites with improved mechanical performance. Specifically, the segmental relaxation dynamics of the healed composite was largely restricted due to increased number of ion-dipole interactions and S-S cross-links at the junction of the cut surface. We envisage that this extraordinary healing property, unreported yet, would be of great importance toward the design of novel NR-SiO2 elastomeric hybrids with superior mechanical properties. © 2019 American Chemical Society.