A study of the complex drying dynamics of polymeric mixtures with optical microscopy and gravimetric measurement is presented. Droplet formation is observed, followed by a collapse that leads to the residual craters in the dried film. The process is followed in situ under well-defined temperature and hygrometric conditions to determine the origin and nature of these droplets and craters. The drying process is usually completed within 1 h. The observations are explained using a simple diffusion model based on experimental results collected from mass and optical measurements as well as Raman confocal microspectrometry. Although the specific polymeric mixtures used here are of interest to the cosmetic industry, the general conclusions reached can apply to other polymeric aqueous solutions with applications to commercial and artistic painting.