The use of nanocomposites as dielectric materials is expected to lead to improved electrical performance. However, recent research has shown that moisture absorption can cause a deterioration in the electrical performance of nanocomposites. Although it is generally accepted that hydroxyl groups attached to nanoparticle surfaces are the main cause of moisture absorption, the impact of this absorption on the electrical properties of nanocomposites is still not fully understood. In this paper, a series of measurements, including thermogravimetric analysis, DC breakdown, surface potential decay and space charge, are conducted with the aim of determining the impact of moisture absorption on the electrical properties of polyethylene/silica nanocomposites. The results show that the loading ratio of nanosilica and the humidity of the conditioning environment determine the amount of absorbed moisture. According to the Zhuravlev model, the main contribution to the deterioration in electrical properties of nanocomposites comes from the large amount of moisture absorbed in multilayer form. It is found that the loading ratio of nanosilica is the most significant factor in reducing DC breakdown strength.