Esters with acyl groups can be formed by the esterification of polyglycerol. The purpose of the present study was to produce fatty acid esters [hexanoic (caproic), octanoic (caprylic), decanoic (capric), dodecanoic (lauric), tetradecanoic (myristic), hexadecanoic (palmitic), octadecanoic (stearic)] and polyglycerol (average number-of degrees of polymerization of 5) with varying degrees of esterification and to examine their emulsifying properties. A number of fundamental catalysts of polyglycerol acylation reactions by methyl esters of carboxylic acid were studied, and sodium methoxide was found to be the best choice. The temperature rate of transesterification increased from 180 to 220 °C with the fatty acid chain alkyl residue. Synthesized mono-, di-, tri-, tetra-, and heptaesters of various fatty acids and polyglycerol provided the highest hydroxyl values from 15 to 815 mg KOH g−1 and saponification values from 82 to 321 mg KOH g−1. The emulsifying properties were assessed for all polyglycerol and fatty acid esters, with results showing maximum emulsifying effect for tri- and tetraesters of capric, lauric, and caprylic acids. Regardless of the hydrophilic–lipophilic balance value (HLB) of polyglycerol esters and carboxylic acid, a 4:1 ratio of sunflower oil to water formed a water-in-oil type emulsion. When mixing oil and water in a 1:1 ratio, mono- and diesters of polyglycerol formed an oil-in-water type emulsion, heptaesters formed a water-in-oil type emulsion, and tri- and tetraesters formed both of types of emulsions, depending on the length of the acid hydrocarbon radicals. © 2016, AOCS.