The crystallinity, particle size and morphology of polyphenylene sulphide synthesized from 1, 4-dibromobenzene and sodium sulphide have been investigated by X-ray diffraction and scanning electron microscopy. It was found that the crystallinity increased from 62 to 68% with an increase in reaction time. A reordering of crystalline structure with increase of reaction time was also noted. The particle size growth was slower as compared to the reaction rate and the distribution was very sharp. The results are compared with those for polyphenylene sulphide obtained from 1, 4-dichlorobenzene and sodium sulphide. © 1990 Chapman and Hall Ltd.