Methyl etherified amino resin is widely used in steel plate and automotive coatings. Since it is hard and brittle, it often needs to be compounded with other film-forming materials to improve the performance. In this study, waterborne acrylic resin was crosslinked with total-methyl etherified amino resin to form a film, and the pyrolysis kinetics of the product under optimal conditions was studied. The kinetic activation energy and pre-exponential factor of thermal degradation were calculated by Kissinger method, Flynn-Wall-Ozawa method and Kissinger-Akahira-Suunose method. In addition, the corresponding thermal degradation mechanism function was deduced by Coats-Redfern method. Comparing the film-forming properties and pyrolysis properties of waterborne acrylic resin before and after cross-linking, it was found that the flexibility, adhesion and thermal stability of the products were improved. This study provides quantitative data for the application of total methyl etherified amino resin in resin matrix.