Converter transformer is the extraordinarily vital apparatus in the high-voltage direct current (HVDC). Transformer oil and oil-impregnated paper are considered as the essential parts of converter transformer, which has suffered various complex electric fields such as AC/DC composite electric field and polarity reversal. The occurrence of discharge or insulation failure in oil-paper insulation system will threaten the safety of the entire grid. Hence, efforts should be focused on investigating the charge behavior and improving the property of dielectric.This chapter presents a study aimed at investigating the influence of different types of nanoparticles on thermal and dielectric properties along with the relation between them and the effects of switching overvoltage on the charge coupling behavior of oil-impregnated paper, and the surface charge behavior on double-layer oil-paper insulation under pulse voltage is investigated.