To fully understand the distribution network cable accessories’ moisture fault, the variation in insulation parameters of the cable main insulation of cross-linked polyethylene (XLPE) and the cable accessory reinforced insulation of silicone rubber (SIR) under different moisture conditions are studied experimentally. Furthermore, the effects of typical moisture defect forms and moisture positions on electric field distributions are studied by establishing the interface defect model. The experimental results show that the insulation properties of XLPE after water immersion are more seriously reduced than SIR. The resistivity of XLPE and SIR specimens decreases significantly with the increase in moisture time, decreasing by 90.3% and 48.3% after 720 h, respectively. The relative dielectric constants of the two kinds of specimens increase with different degrees after moisture, increasing by 5.16% and 7.83%, respectively, and the breakdown strength decreases by 18.3% and 13.1% after 720 h, respectively. The simulated results show that the moisture form and position have a great influence on electric field distribution. The electric field distortion caused by water trees’ defect is the most serious, followed by water film defects and water droplet defects. Besides, for different types of moisture defects, the position of the maximum distortion electric field is different.