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Low density polyethylene film surface-grafted phenolic resole was prepared by a sequential processes. Firstly, acrylic acid was grafted to the surface of low density polyethylene by photo-grafting. Secondly, the carboxylic groups in poly(acrylic acid) chains were transferred to sulfonic groups by the reaction of carboxylic groups with sulfanilic acid. Finally, a thin layer of phenolic resole was cured onto the surface of low density polyethylene. The grafting process was characterized by FTIR-ATR and gravimetric analysis. A possible model was proposed to interpret the experimental results.