The effects of oxidative degradation on the performance of crosslinked polyethylene pipes were analyzed by the investigation of tensile properties and chemical structure change of the pipes during oxidative degradation. Annealing at high temperatures or UV irradiation method was used to induce the oxidative degradation of the crosslinked polyethylene pipes and the effects of the die temperature on the oxidative degradation of the pipes were also investigated. The tensile properties and chemical structure change of the pipes were investigated by universal testing machine and FT-IR, respectively. With the progress of thermo-oxidative degradation the tensile strength of the pipes slowly decreased but the elongation at break rapidly decreased, and the chemical structure of the pipes also changed considerably because of the introduced oxygen molecules. These results would be useful in estimating the performance deterioration of the crosslinked polyethylene pipes due to the oxidative degradation during production and storage.