In this paper, the measurement of the crosslinking percentage (gel volume fraction) of polyethylene materials by using DSC technique is presented. To obtain the calibration curve, the networked samples of ASTMD 2765-01 corresponding to the curves of pure melt samples at the start of the reaction were used. The resulting calibration curve was used to predict the percentage of polyethylene cross-linked in a continuous process, and these results were compared with those obtained from D 2765-01, which resulted in excellent agreement between the two states. This technique is faster and cheaper and requires less raw material, the product does not release any harmful substances and is ASTM correct.