The hollow polymer spheres preparation technique of micro-encapsulation requires quantative and precise understandings of the complex evaporation, gelation and solidification processes of the polymer solution. This study focused on the mass transfer during the evaporation-gelation process of a PS-benzene solution inside a Stefan tube. Liquid level reductions of polymer solutions were accurately measured using an image-recognition method with 50μm accuracy. An evaporation model was developed to successfully predict the variation of liquid level, concentration and mass transfer flux, considering solution activity and density as lumped parameters that depend on concentration. This carefully validated evaporation model is expected to be invaluable for the analysis and design of polymer solution evaporation, accommodating various geometries and boundary conditions. Despite the observation of complex processes such as precipitation of polymer molecules and solution-gel phase separation, we characterized and explained them using the effective concentration-density relation. The study showed that reaching a mass fraction of benzene of 0.6 is a significant event in the evaporation process, indicating the end of gelation and the beginning of solidification.