The orientational structure of the friction-transferred poly(tetrafluoroethylene) (PTFE) film, which consists of highly oriented polymer strands, was evaluated with energy-dispersive total-reflection X-ray diffractometry. In the film, each PTFE molecule is oriented along the friction direction, and PTFE crystallites have a preferred orientation with respect to the substrate surface. The orientational distribution of the chain direction was quantitatively evaluated. The half-width of the distribution was determined to be about 3 degrees. The dependence of the orientational distribution on temperature is discussed. (C) 2001 John Wiley & Sons, Inc.