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Ionomer polyesters have polymer backbones functionalized with charged groups that make them water-dispersible. Despite the widespread use of ionomer polymers in environmentally friendly coatings without volatile organic solvents, the fundamental understanding of their film formation properties is still limited. In the study, we deposited polyester nanofilms of brilliant structural colors and correlated the macroscale optical properties to the microscale thickness of the thin films. We found that sessile water droplets deposited on these films drive the formation of a rich variety of structures by an evaporation-induced effect of “coffee-ring erosion”. The ionomers spontaneously get partially re-dispersed in the form of nanoparticles in the sessile droplets and driven by convective evaporation flows, become redistributed in multiple colorful ring patterns. By using the structural colors as means to follow the polymer redistribution, we characterized further the coffee-ring patterns and found that the generated patterns are dictated by polymer composition but are mostly independent on molecular weight. As expected by colloidal theory, this phenomenon was suppressed in presence of electrolytes. Furthermore, we show that the integrity of these thin polyester films can be significantly improved by thermal densification without any further chemical curing.