To reveal the wear mechanism of hyperbranched polysilane (HBPSi) grafted multi-walled carbon nanotubes (HBPSi–MWCNTs) modified benzoxazine–bismaleimide (BOZ–BMI) resin (HBPSi–MWCNTs/BOZ–BMI), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) were employed. The results indicated that the suitable addition of HBPSi–MWCNTs could largely enhance the tribological properties of BOZ–BMI composites. The worn surface of the composites showed that the severe wear of the BOZ–BMI resin was converted from adhesive wear to abrasive wear with the addition of HBPSi–MWCNTs. The excellent tribological properties can be attributed to the improved interfacial adhesion between HBPSi–MWCNTs and the BOZ–BMI resin matrix. The TGA demonstrated that the composite with 0.8[Formula: see text]wt.% HBPSi–MWCNTs exhibits better thermal resistance; thus, it can inhibit adhesive wear during the friction process. The XPS spectra and the surface energy showed that the HBPSi–MWCNTs could be exposed on the worn surface of the composite to improve the anti-wear capacity of the composites further.