This paper discusses the effect of doping of electro-insulating liquids with nanoparticle materials on the thermal properties of the obtained nanoliquids and heat transport in the transformer. Mineral oil, synthetic ester, and natural ester were used as base liquids. The effectiveness of doping base liquids with nanoparticles was supported by ultraviolet-visible (UV/VIS) measurements. In turn, Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) confirmed the absence of intermolecular interactions (i.e., hydrogen bonding). The influence of modification of electro-insulating liquids with fullerene C60 and titanium dioxide TiO2 nanoparticles on such thermal properties as thermal conductivity, specific heat, kinematic viscosity, density, and thermal expansion was investigated. Based on these properties and the theory of similarity, the cooling efficiency of the transformer filled with the analyzed nanofluids was determined. Nanofluids’ cooling effectiveness was compared with the cooling effectiveness of the base liquids. This comparison was supported by an analysis of Grashof, Prandtl, and Nusselt numbers. It has been shown that the modification of electro-insulating liquids with nanoparticles widely used in order to improve their dielectric properties, such as C60 and TiO2, does not have a significant influence on their thermal properties. The addition of fullerene C60 caused an increase in kinematic viscosity, which was compensated by the increase in specific heat. In the case of TiO2, the addition of this nanoparticle resulted in an increase in kinematic viscosity and a decrease in specific heat, which were balanced out by the increase in thermal conductivity. In summary, the heat exchange-capacity of liquids did not change due to doping with nanoparticles.