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Many detailed studies were carried out on polymer micro/ nanocomposites that are used in high-voltage applications. The study was based on a lot of previously published research work on the field. Particular focus is on the structure-property relationship of composite materials used in power engineering, by exploiting fundamental theory as well as numerical/analytical models and the influence of material design on electrical, mechanical and thermal properties. In addition to describing the scientific development of micro/nano-composites electrical features desired in power engineering, the study is mainly focused on the electrical properties of insulating materials, particularly cross-linked polyethylene (XLPE) and epoxy resins, unfilled and filled with different types of filler. Polymer micro/ nanocomposites based on XLPE and epoxy resins are usually used as insulating systems for high-voltage applications, such as: cables, generators, motors, cast resin dry-type transformers, etc.