Ester group interactions with each other and with the atoms between them were investigated in order to determine dependence of chemical and thermal stabilities of aliphatic diesters on structure. Novel glycol-derived diesters with chemical formula (C17H33COO)(2)CnH2n were used as model systems. Chemical stability was determined using H-1 NMR and FTIR, and thermal stability and weight-loss kinetics were examined using nonisothermal TGA. Chemical stability increased with the number of methylene units (n, carbon) between the ester groups until n = 6, and no significant improvement was observed past n > 6. It is argued that other ester-dense materials, including polyesters, would behave similarly. Evidence of a strong dependence of thermal stability on chemical stability is also provided. This work shows that the chemical and thermal stabilities of ester-dense functional materials such as diesters, oligoesters, and polyesters can be manipulated by varying the distance between the ester groups, and hence the interactions of the electron-withdrawing ester groups with its neighbors.