The paper presents the results of comparative studies of thermal properties of various types of natural esters used as electroinsulating liquids in transformers. Adequate thermal properties of electro-insulating liquids ensure reliable work of transformers. Two natural esters were selected for the study – one commonly used in distribution transformers, the other characterized by low viscosity. Fourier Transform Infrared Spectroscopy and UV-Visible spectroscopy were used to examine the chemical structure of the examined esters. Properties such as thermal conductivity coefficient λ, kinematic viscosity υ, specific heat cp, density ρ, and thermal expansion coefficient β were analyzed. Heat transfer factor α of the liquid was calculated on the basis of obtained properties. This factor defines the ability of an insulating liquid to heat transport in the transformer, thus determining its reliability. The authors put forward a thesis that a low viscosity natural ester will have a higher heat transfer factor α due to its low viscosity, which affects the factor α. The analysis of thermal properties was carried out for the following temperatures: 25, 40, 60, and 80°C. On the basis of the calculated factor α, the temperature drops in the transformer filled with the analyzed types of natural esters were determined. It has been shown that if a low viscosity natural ester is used in the cooling system of the transformer, the temperature of the hot-spot will be lower. This fact may contribute to more reliable work of transformers and extend its service life.