A detailed structural investigation of a promising bio-based polymer, polyglycerol citrate poly-ester, obtained by bulk polycondensation of glycerol (Gly) against citric acid (Cit) under mild reaction was performed. This polymer was suggested to be well suited for coating seeds or similar agricultural applications. The reaction in conditions with and without catalyst use (sulfuric acid, H2SO4) was investigated, showing evidence that it is possible to modify the polymer solubility according to the ratio and catalyst utilization. 13C and 1H NMR indicated that synthesis catalyzed with Cit excess leads to higher esterification degrees of citrates groups. In contrast, the Gly moi-eties are more prominent in catalyzed polymers regardless of the excess monomers. Overall, a successful conversion of Gly and Cit into polyesters was attained, even without catalysis, enabling a simple route for large-scale production of this green material to be used as coating material. Tests on soybean seed coating with a PGCit solution of 75% indicated that the seed quality and ger-mination rate was not affected by PGCit coating, concluding that this polymer is promising for this application.