Vitrimer composites with bond- exchange reactions offer significant advantages in terms of repair and recyclability. The mechanical properties of such composites can be designed by modifying the epoxy/anhydride ratio, thus allowing their interface properties to be customised. In this study, the mode-I interfacial fracture properties of vitrimer carbon fibre composites with different epoxy/anhydride ratios are investigated experimentally and numerically. The results show that composites with an epoxy/anhydride group ratio of 1:0.5 exhibit the highest fracture toughness, with a maximum value of 1.6 mJ/mm2. Meanwhile, the analysis of the composites’ microscopic fracture morphology indicates their good bonding performance with carbon fibres. Subsequently, a multiscale numerical approach is developed to simulate the mode-I fracture response of composite laminates and establish a trilinear cohesive model to simulate the macroscopic interfacial fracture behaviour. In this approach, a matrix elastic–plastic constitutive model and the J-integral method are applied to obtain the stress distribution in the fibre-bridging phase via a double cantilever beam fracture test. The macroscopic fracture behaviour obtained via simulation is consistent with the experimental results. Therefore, the proposed multiscale numerical simulation method, which correlates the matrix properties with macroscopic fracture parameters, allows the interlaminar properties of composites with novel matrices to be evaluated effectively.