The relationship between solvent-crystallized morphology and glass transition characteristics of polyp-phenylene sulphide) that had been previously processed with 1-chloronaphthalene is reported. Dielectric relaxation studies revealed a strong positive offset in glass transition temperature (T-g) of the solvent-crystallized samples compared to the corresponding amorphous sample, as well as thermally crystallized samples of similar bulk crystallinity. Additionally, the apparent activation energy for the a-relaxation was higher for the solvent-crystallized case. The dielectric relaxation strength (Delta epsilon = epsilon (0) - epsilon (infinity)) determined for the solvent-crystallized PPS is small and showing weak temperature dependence, leading to an increase in De as the temperature increased above T-g. This was explained by the existence of a large amount of tightly bound, or rigid-amorphous materials in the solvent-treated sample. We suggested that the large amount of immobile amorphous material, and its ability to relax at temperatures above T-g, is related to strong secondary crystallization process in solvent-treated PPS.