Thermoset acrylic–melamine resins are widely used for automobile exterior coatings. These materials are formulated by reacting an acrylic polyol with an alkylated melamine. Because the reactions are reversible, acrylic–melamine coatings tend to hydrolyze during exposures in moist environments. During hydrolysis, water in the coating film is consumed. To keep the moisture content in the film in equilibrium, water must be transported from regions of high water concentration to regions of low water concentration. An approach based on Fourier transform infrared (FTIR) spectroscopy analysis of the coating degradation fitted to a transport model is presented to estimate the diffusion coefficients and velocities of water transport during the hydrolysis of an acrylic–melamine coating exposed to different relative humidities (RHs). Theoretical prediction agreed well with the experimental FTIR data of coating hydrolytic degradation. Generally, both the diffusion coefficient and velocity of water transport in the coating increased with increasing RH. Since water transport resulting from the hydrolysis reactions is a very slow and complex process, the approach presented here provides a viable means for obtaining valuable data for quantitative analyses of coating hydrolytic degradation at different RHs.