The thermal behavior of a solution-cast liquid-crystal line polymer (LCP) film was extensively studied by positron-annihilation lifetime spectroscopy (PALS). From the positronium (Ps) lifetimes of the first heating process from 40 to 250 degrees C at a heating rate of 2.5 degrees C/h, four characteristic temperatures (140, 170, 200, 235 degrees C) were observed. From a combined investigation with conventional differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), the first three characteristic temperatures were found to correspond to reorientation. glass-transition, and softening temperatures, respectively. The fourth temperature was related to the commencement of crystallization, which was observed above about 235 degrees C from a decrease in the Ps lifetime. A low-temperature PALS experiment exhibited the gamma-transition due to rotation of the phenyl moiety at about -53 degrees C. (c) 2005 Elsevier Ltd. All rights reserved.