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Multivesiculated polyester particles (MVPs) are obtained by reticulation of a double emulsion system formed by a polyester/styrene solution dispersed in an aqueous colloidal solution. During its synthesis, the acid/base reaction between polyester carboxylic end groups and an added amine plays an important role in stabilizing the two emulsion systems (water-in-oil and oil-in-water). This work studies the influence of diethylenetriamine, aminoethylethanolamine, diethanolamine, and triethanolamine on MVPs' average particle size, vesiculation morphology, dry film opacity, and yellowing. The particular aspects observed for each amine are discussed, allowing identification of the relevant mechanisms taking place in the formation of MVPs. POLYM. ENG. SCI., 53:2261–2269, 2013. © 2012 Society of Plastics Engineers