The widespread use of cross-linked polyethylene (XLPE) as insulation in cables may be attributed to its outstanding mechanical and dielectric properties. In order to quantitatively evaluate the insulation status of XLPE after thermal ageing, an accelerated thermal ageing experimental platform is established. Polarization and depolarization current (PDC) as well as elongation at break of XLPE insulation under different ageing durations are measured. XLPE insulation state is determined by the elongation at break retention rate (ER%). Based on the extended Debye model, the paper proposed the stable relaxation charge quantity and the dissipation factor at 0.1 Hz to evaluate the insulation state of XLPE. The results show that the ER% of XLPE insulation decreases with the growth of ageing degree. The polarization and depolarization current of XLPE insulation will increase obviously with thermal ageing. Conductivity and trap level density will also increase. The number of branches of the extended Debye model increases, and new polarization types appear. Stable relaxation charge quantity and dissipation factor at 0.1 Hz proposed in this paper have a good fitting relationship with ER% of XLPE insulation, which can evaluate the thermal ageing state of XLPE insulation effectively.