The thick insulation layer of 110 kV XLPE power cables will result in the gradient changing morphology with the radius due to crosslinking process and cooling of the XLPE insulation. In this paper, the morphology of cross-linked polyethylene (XLPE) insulation of 110 kV cable and the uniforming effect of the heating process on it are researched by the differential scanning calorimetry (DSC) and X-ray diffraction (WAXD). The middle layer morphology structures of insulation produced by normal technology are of better uniform, while the crystallinity of the inner and outer layer of the insulation is lower than that of the middle one.The melting enthalpy △Hm of materials displays the difference of the crystal morphologies sensitively. The difference of crystallizing morphology in different layers of the high-voltage power cable insulation can be improved by heating process. But the uniforming of morphology of the insulation by heating process requires sufficient temperature and time. The effect of the on-line stress-relaxation equipment used widely by cable works now should be doubted. The test results of WAXD reveal that thermal stress changes the interplanar distances in the crystal region. So the radical stress in the insulation is tensile mainly.