AbstractCO, CO, and C(O)O oxygen‐containing groups were introduced onto the molecular chain of high‐density polyethylene (HDPE) through ultraviolet irradiation in air. The introduction rate of the oxygen‐containing groups onto HDPE increased with increasing environmental temperature. After ultraviolet irradiation, the molecular weight of HDPE decreased, and its distribution became wider; the melting temperature, contact angle with water, and impact strength decreased; the degree of crystallinity and yield strength increased; and their variation amplitude increased with environmental temperature. The environmental temperature had an effect on the gel content of irradiated HDPE. HDPE‐irradiated for 48 h at 35° and 50°C were not crosslinked. However, gelation took place in HDPE irradiated for 24 h at 70°C. HDPE irradiated at a high environmental temperature was more effective than that irradiated at a low environmental temperature in compatibilizing HDPE with PVA. Compared with the 83/17 HDPE/PVA blend, the yield and notched impact strength of the 73/17 HDPE/PVA blend compatibilized with 10% HDPE irradiated for 24 h at an environmental temperature of 70°C increased from 30.8 MPa and 110 J/m to 34.9 MPa and 142 J/m, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2966–2969, 2003