For the environmental, economic or technical reasons, oils based on natural esters were used to replace mineral oil in electrical equipments in low and medium voltage. This work consists on characterization of a mixture (RS50) of low viscosity natural esters based on rapeseed oil for applications in high voltage transformers. The influence of humidity, temperature, particle content and thermal aging on its dielectric properties such as permittivity, conductivity, losses and electrical strength was highlighted. The RS50 has a high water solubility, its conductivity, permittivity and losses are both higher than those of mineral oil but these differences are reduced in aged oils. Its electrical strength is similar to mineral oil even after aging. However, an analysis more precise of prebreakdown and breakdown phenomena in specific configurations have shown that natural esters are less favourable for high voltage applications than mineral oil. In parallel, a methodological study was carried out. Advantage of using the frequency spectroscopy measuring method for the characterization of insulating liquids is highlighted. The validity of conditions for the dielectric strength measurement in the liquid insulation, which is traditionally imposed following the standards, was also discussed.