The degradation of mechanical properties of PE pipe materials caused by hot oxygen aging will inevitably reduce the service life of the pipe, which is a serious hidden danger to social and economic development and people's life and property safety. A nonlinear ultrasonic evaluation method for thermo-oxygen aging pipes was proposed. The nonlinear ultrasonic detection signals of PE pipes were extracted by building a nonlinear ultrasonic detection system for water immersion, and a correlation model between the characteristic parameters of nonlinear ultrasonic detection and elongation at break and fracture stress was established. The nonlinear ultrasonic detection mechanism was revealed by observing the micro-structure changes of PE pipes after aging. The experimental results show that the elongation at break and profit at break of PE pipe materials decrease with the increase of the nonlinear coefficient. The surface micro-cracks, holes and folds formed after the aging of the pipe are the main reasons for the mechanical degradation of the pipe and the increase of the nonlinear ultrasonic detection coefficient. The nonlinear coefficient can be used to evaluate the mechanical degradation of the pipe caused by thermal oxygen aging.