Power cables are widely used in various fields of power transmission, and cable accessories are the weakest link in power cable systems due to their complex structure and multi-layer insulation coordination issues. This paper investigates the changes in electrical properties of the silicone rubber/cross-linked polyethylene (SiR/XLPE) interface at high temperatures. The physicochemical properties of XLPE material under thermal effects with different times are characterized through FTIR, DSC, and SEM tests. Finally, the mechanism of the effects of the interface state on the electrical properties of the SiR/XLPE interface is analyzed. It is found that with the increase in temperature, the changes in electrical performance of the interface do not show a monotonic downward trend, while interestingly, they can be divided into three stages. Under the thermal effects for 40 d, the internal recrystallization of XLPE in the early stage improves the electrical properties of the interface. In the later stage of thermal effects, the amorphous region inside the material is severely damaged and the molecular chains are severely broken, resulting in a decrease in the electrical properties of the interface. The results above provide a theoretical basis for the interface design of cable accessories at high temperatures.