The commonly held perception that high conductivity in conducting polymers is linked to a high level of pi-stacking order in the material is shown here to be of lesser importance in highly conducting poly(3,4-ethylenedioxythiophene) (PEDT), which has been prepared by chemical vapour phase polymerisation. Despite the fact that there is a highly energetic phase transition about 130 C (110 J/g), and that this transition corresponds to a loss of the long-range pi-stacking as observed in grazing angle XRD, the conductivity remains unchanged beyond the transition and only decreases by a factor of two when heating to above 200 C. The XRD data suggest that order in two dimension remains above the phase transition measured by DSC and this order is sufficient to maintain a high level of electronic conductivity. Furthermore, as the ligand on the iron salt used in the synthesis is varied, the conductivity of the PEDT varies over two orders of magnitude. These phenomena cannot be explained by different degree of doping or crystallinity and it is proposed that the iron salt has an ordering effect during the vapour phase polymerisation. (c) 2007 Elsevier Ltd. All rights reserved.