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.