We report the development of an intrinsic healing glass fibre reinforced polymer (GFRP) composite based on a disulphide-containing organic-inorganic thermoset matrix. Thermomechanical experiments showed that the newly developed matrix has a combination of a Young's modulus value in the range of (800–1200 MPa), the ability to multiple thermally induced healing delamination (70–85 °C), and processability by conventional vacuum infusion process that is not yet reported in literature. The composite mechanical properties and the extent of healing were determined by flexural, fracture and low-velocity impact testing. Small sized (<cm2) damage could be partially healed multiple times using a minimal healing pressure to ensure a good alignment of the damaged interfaces. The level of healing can be enhanced, even for large (>cm2) damage, by increasing the healing pressure provided the location of the primary damage is concentrated within the matrix phase. The polymer matrix composite introduced here represents a significant step forward from the often mechanically inferior intrinsically self-healing composites towards structural self-healing composites.