Aging treatments in water and in air and controlled neutron irradiation were performed on commercial crosslinked lowdensity polyethylene (XLPE) for promoting different mesostructural arrangements of crystallites and crosslinking degree. Infrared spectroscopy, differential scanning calorimetry, differential thermal analysis, thermogravimetry, and dynamic mechanical analysis were used as characterization techniques. The relaxation peak related to the mobility of the grain boundaries from crystalline zones in XLPE was identified at around 260 K (at 7 Hz), involving an activation energy of 90 AE 4 kJ mol −1 . The usual equation for describing the grain boundary mobility in metals involving the movement of grain boundary dislocations was adapted for studying the mobility of the boundaries among the crystalline zones, successfully. In addition, a new mechanical relaxation peak that appears at around 300 K (at 7 Hz), which involves an activation energy of 94 AE 5 kJ mol −1 , was found. The driving force controlling this peak was determined as the dragging of the polymer chains at the amorphous zones adjacent to the crystals controlled by the mobility of the crystallites boundaries. The chains movement was done with break away from the physical pinning points.