In order to improve the performances of urea-formaldehyde (UF) resin adhesive and reduce formaldehyde emission, the isocyanate was applied to modify the UF resin adhesive. The effects of the composition ratio of the isocyanate/UF resin on the thermal stability and molecular structure of the composite adhesive were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analyzer. The results showed that the appropriate addition of the isocyanate into the UF resin is favorable to improve the performances of the composite adhesive due to the chemical cross-linking reaction of the isocyanate with UF. Furthermore, the reaction mechanism of the UF resin adhesive with isocyanate was analyzed in detail. These research results can be applied to aid materials engineering design for the development of new adhesive, quality assurance, and characterization assessment of durability.