An NMR investigation of poly(trifluoroethylene) is reported. Using known assignments of the fluorine solution-state spectrum, the defect level has been determined as well as a high degree of atacticity confirmed. The solid-state (FNMR)-F-19 study concentrated on the detection of heterogeneities in the polymer. Transient oscillations in H-1 --> C-13 CP curves have been used in order to determine effective bond distances and, consequently, to detect motion of the polymer chain. The onset of motion has been confirmed by comparing the measured axially symmetric fluorine shielding tensor with the asymmetric tensor obtained from ab initio calculations carried out on the rigid molecule. (C) 2000 Elsevier Science Ltd. All rights reserved.