Cross-linked polyethylene (XLPE) cable is a representative power transmission cable. XLPE has excellent mechanical properties, chemical and heat resistance, and insulation. However, XLPE insulation deteriorates during operation due to electrical, mechanical, and thermal stresses. Among these, thermal stress is a major factor and reduces insulation properties due to a change in molecular structure. Therefore, XLPE characteristic evaluation by heat exposure is essential for power cable condition evaluation. Herein, deteriorated XLPE samples were characterized by tensile strength, X-ray diffraction, Fourier-transform infrared spectroscopy, differential scanning calorimetry, and ultraviolet-visible spectroscopy after exposure to various temperatures and durations. Comparing the tensile strength with other analysis results yielded correlations. Each characteristic showed a linear relationship. The correlation between tensile strength and carbonyl index was the strongest, and the coefficient of determination, R2, was 0.9299. Therefore, these results will provide important information on chemical properties when establishing operational management standards for XLPE insulators in the future.