AbstractThe relaxational behavior of CR‐39 (poly allyl diglycol carbonate) nuclear track detectors was determined over a large temperature range (−100 to 125°C) including the glassy, glass transition, and ionic conduction regions by means of dynamic mechanical and dielectrical measurements, differential scanning colorimetry, linear coefficient of expansion, and especially thermally stimulated current methods owing to their high sensitivity and resolving power. This investigation was carried out as a first step aimed, on the one hand, at finding possible correlations between dosimetric performances, polymer morphology, and intrinsic or extrinsic relaxations and, on the other hand, at determining the origin of the inconsistent background and response properties, which are still a serious obstacle to the use of this material as a personnel dosimeter in spite of its high sensitivity and wide response range. Six distinct relaxation regions have been evidenced, most of which being to some extent dependent on the sample investigated and its thermal history. From higher to lower temperatures, these various relaxations have been ascribed to charge carrier migration over macroscopic distances (ρ), glass transition (α), nonequilibrium precursor motions of the glass transition (ά), and local mode motions of the diethylene‐glycol dicarbonate links (β), diethylene glycol segments (γ), and carbonate groups (δ). In addition to these intrinsic relaxations, the as‐received samples are also characterized by small‐scale residual stresses that relax out irreversibly at temperatures lower than the glass transition temperature Tg. The systematic study of the influence exercized by the position of a specimen in a given sheet, and, for a given sample, by annealing, thermal cycling, and physical aging on relaxation properties shows that, besides spatially inhomogeneous internal stresses, cross‐linking density, and cluster morphology, marked structural modifications and nonequilibrium processes can occur by heating the polymer above Tg. These phenomena deserve a great deal of consideration because they could be key points for identifying the sources of the troublesome fluctuations of dosimetric response. Relaxation studies thus appear as useful and sensitive tools for a deeper understanding of the performance of CR‐39 polymer as a track recorder.