This paper presents the influence of thermal ageing on the physico-chemical and electrical properties of 500 kV extra high voltage direct current (EHVDC) XLPE cable insulation. EHVDC XLPE cable sections are placed in a thermal oven and thermally aged at 106 °C (melting peak temperature) for 250, 500 and 1000 h. After ageing, the inner, middle and outer layers of the cable insulation are characterized by Fourier transform infrared (FTIR) spectroscopy, oxidation induction time, X-ray diffraction (XRD), space charge, DC conductivity and DC breakdown measurements. The physicochemical analysis results show that the cross-linking by-products in the cable insulation are difficult to be completely removed during the ageing process, whereas the thermal ageing cannot completely consume the antioxidants in the materials. The space charge measurement results show that the hetero charges are accumulated inside the unaged middle layer samples. However, the space charge accumulation and electrical conductivity of the samples are significantly reduced after 1000 h ageing. Moreover, the DC breakdown strength of the inner and middle layer samples is continually increased with the increase of the ageing time. It is elucidated that the thermal ageing leads to the re-crystallization and re-degassing of samples, improving the space charge behavior and the charge carrier trapping phenomenon. It is proposed that the temperature of 106 °C could be used as a suitable degassing temperature for the EHVDC XLPE cable production.