Polycaprolactone (PCL) was gamma-irradiated at different phases such as solid state at 30 to 55 degrees C, molten state, and supercooled state, under vacuum or air atmosphere, to elucidate its crosslinking behavior. Irradiation in the molten state (80 degrees C) gave higher gel content compared to room temperature. The resulting gel, however, contains many voids due to the gas evolved during irradiation. Conversely, irradiation of PCL in the supercooled state led to the highest gel content among the three irradiation conditions and it was free of voids. Based on these findings, to evaluate heat resistibility of crosslinked PCL prepared by irradiation in supercooled state, the crosslinked PCL was hot pressed at 200 degrees C to form a film. Unirradiated PCL melted at 60 degrees C. The film prepared from 160 kGy irradiated PCL (crosslinked sample) under an applied load of 0.667 MPa, at a temperature of 110 degrees C did not break even after 3 h. At a temperature of 120 degrees C, the film has a tensile strength of 3 MPa. Furthermore, the film extended by hot pressing is transparent and has high heat shrinkability.