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In this paper, an investigation was performed to study the influence of irradiation heat on the structure and thermal properties of PTFE samples. The tribological properties of POM/irradiated‐PTFE composites were also compared. The results revealed that shortening the interval time of irradiation could induce higher surface temperature and produce more carboxyl groups and trifluoromethyl groups. Additionally, these bulky groups were partly incorporated into the crystalline region of PTFE, which increased the lattice parameters. The decreased interval time accelerated chain scission reactions, causing the Tm and T5% of irradiated PTFE with interval time of 6 min dropped by 12.1 and 107.6°C, respectively, compared with the unirradiated PTFE. More importantly, the POM/A1600 (weight ratio of 90/10) composites were endowed with the lowest friction coefficient of about μ = 0.129 due to the highest transfer film content formed on the friction pair after sliding. The study of the influence of irradiation heat on the degradation of PTFE could provide some theoretical basis for optimizing the electron beam irradiation process and achieving the controllable design of high degradable PTFE. This research could provide a new idea for the utilizing of irradiation heat in the fields of material modification.