The addition of microsized fillers to polymers, in order to tailor their properties, has been extensively used in many industrial applications since the 1960s. The same approach applies to the field of electrical insulation. Epoxy resin is a widely used polymer in the electrical power sector, but it is usually loaded with microsized fillers, such as aluminum oxide and silicon dioxide, mainly to increase its thermal conductivity, improve its mechanical properties, and to decrease cost. Polymers with microsized fillers are called microcomposites. In the mid-1990s, a new type of polymeric composites for high voltage applications, the so-called nanocomposites, emerged. The main characteristic of these composites is the small filler size, which is smaller than 100 nm at least in one dimension. Since then, there has been a growing interest in the performance of polymeric nanocomposites for high voltage applications, including epoxy nanocomposites. The performance of nanocomposites is mainly related to the tremendous effective internal surface area of these materials because of the high surface-tovolume ratio of nanofillers. After 20 years of research, a significant amount of data has been generated which reflects the potential of nanodielectrics. It has been shown that nanofillers are capable of contributing to the improvement of both the thermal and electrical properties of polymers. However, the laboratory performance of nanocomposites is inconsistent and unpredictable. These are the main factors which inhibit the applicability of nanodielectrics. Important challenges in the field of epoxy nanocomposites should be overcome before nanodielectrics can be produced on an industrial level. The most important challenge is related to the dubious reproducibility of the nanocomposite performance which is closely related to sample homogeneity. Thus, the effectiveness of separating the nanoparticles from each other and the homogeneous incorporation of them into the polymer matrix are expected to affect the performance of nanocomposites. However, the extent to which the behavior of nanocomposites is influenced by sample homogeneity is not well defined. In this thesis, a number of epoxy nanocomposites and mesocomposites were synthesized aiming at the analysis of the parameters which influence their thermal and electrical properties. The analysis includes the thermal and electrical conductivity, dielectric response, and breakdown strength under both AC and DC electric fields. The experimental results demonstrate the important role of interfaces in the behavior of epoxy nanocomposites. Based on the experimental results, important parameters for determining the performance of nanocomposites are suggested to be the polymer re-organization and water uptake. The former is related to the influence of nanofillers on the polymer structure, i.e., the areas in the vicinity of nanofillers are assumed to exhibita different behavior from the rest of the polymer matrix. The uptake of water is related mainly to the hydrophilic nature of nanofillers and plays a significant role in the electrical performance of nanocomposites. Apart from the aforementioned mechanisms, the presence of structural imperfections should not be neglected as they affect both the thermal and electrical properties of epoxy nanocomposites. Additionally to the experimental part, models were developed for both the relative permittivity and thermal conductivity of nanocomposites. The models are based on the two aforementioned parameters; polymer re-organization in the vicinity of nanofillers and water uptake due to the hydrophilicity of nanofillers. The main characteristic of both models is the use of the same structure which strengthens the validity of the assumptions. The experimental results are in good agreement with the model results. Also, a large part of the thesis is devoted to the evaluation of the influence of sample homogeneity on the performance of nanocomposites. For this purpose, nanocomposites with different synthesis techniques were fabricated. The results suggest that the thermal conductivity, dielectric response, and breakdown strength (AC and DC) of epoxy nanocomposites are not significantly influenced by the nanoparticle distribution. This observation suggests that high levels of reproducibility can be achieved when the particles are similarly dispersed and differently distributed. Finally, hybrid composites which combine both microsized and nanosized fillers were fabricated, tested, and analyzed. This type of composites is more likely to be employed in industry as epoxy resin in its pure form is rarely used for high voltage applications. It is usually reinforced with high loadings of microparticles. Microcomposites reinforced only with a small amount of nanofillers, i.e., less than 1 % by volume, show a significant thermal and electrical improvement.