With the rapid development of the 5G era and smart homes, self-healing and self-powered smart fire sensors are considered a promising solution for emerging applications, but fabricating such sensors remains a great challenge. In this study, a highly efficient dynamic crosslinking strategy was developed to construct a self-healing organic–inorganic hybrid material (OIH). More precisely, self-healing OIHs were fabricated through a simple Schiff reaction between chitosan and a Ti3O5 metal–insulator transitional material. The incorporation of multi-crosslinked networks (CN, hydrogen bonds, electrostatic interactions) provided stable charge migration paths for the free movement of protons and hot electrons. Accordingly, the OIH exhibited a substantially enhanced fire-response sensitivity (1.09 s). Moreover, this OIH was capable of self-healing while recovering its fire-warning properties. The OIH intelligent system exhibited good universality on various substrates, such as wood, paper, fiberglass fabrics, and polyurethane (PU) foam. By introducing a self-healing OIH into a fire alarm platform, a highly sensitive warning signal can be sent via Wi-fi or Internet applications. Moreover, a self-powered fire-warning system with triboelectric nanogenerator (TENG) is also demonstrated using OIH. The concept of combining a self-healing and self-powered fire-sensing system may provide potential solutions for applying OIH in emerging applications.