This paper aims to investigate the influence of thermal aging on a crosslinked polyethylene (XLPE) cable, and the relationships between the macroscopical high-voltage dielectric and the microscopical physicochemical properties are also elucidated. To better simulate thermal aging under working condition, the medium-voltage-level cable is subjected to accelerated inner thermal aging for different aging times. Then, high-voltage frequency domain spectroscopy (FDS) (cable sample) and analyses of microscopic physical and chemical properties (sampling from the cable), including Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and elongation at the break (EAB), are conducted at different cable aging stages. The dielectric test results show that after a certain aging time, the high-voltage FDS curves of the cable have layered characteristics, and this phenomenon is more obvious as the aging degree increases. Moreover, the slope and the integral of the high-voltage FDS curves rise with aging time. The mechanism is deduced by the physicochemical results that thermo-oxidative aging results in increasing polar groups and dislocation defects in the crystal region, which leads to the above phenomenon. On the one hand, the appearance of polar groups increases the density of the dipole. On the other hand, the destruction of the crystal region increases the probability and amplitude of dipole reversal. In addition, the breaking of molecular bonds and the increase in the amorphous phase also reduce the rigidity of the XLPE molecular main chain. The above factors lead to obvious delamination and larger dielectric parameters of the thermally aged cable. Finally, according to the experimental results, an on-site diagnosis method of cable insulation thermal aging based on high-voltage FDS is discussed.