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It is believed that space charge build-up in cross-linked polyethylene (XLPE) insulation is the main cause of premature failure of underground power cables. The space charge activities in XLPE depend on many factors such as additives, material treatment, ambient temperature, insulator/electrode interface, etc. Degassing is the process of subjecting the XLPE to a moderately high temperature, thereby removing volatile residual by-products and additives that are commonly employed in cable manufacturing to improve insulation performance. While there have been reports comparing space charge activities (as-received) un-degassed and degassed samples, little attention has been placed on degassing conditions effect on space charge. In this paper, investigations of morphology and space charge distribution of planar XLPE samples was carried out as parameters such as degassing temperature, degassing duration and sample thickness were adjusted. Changes in the morphological structure of the material were probed with the differential scanning calorimeter and the transmission electron microscopy, whereas space charge distribution of the samples subjected to DC electric stress was monitored for 24 h using the laser induced pressure pulsed technique. It was revealed that degassing temperature, duration and the thickness of the degassed sample has a direct effect on the morphological structure and space charge distributions of the samples. It is believed that the presence and amount of by-products takes precedence over the morphology of the material as far as space charge evolution is concerned.