A film of poly(vinyl chloride) (PVC) was stretched at 90 degrees C under an inert atmosphere to an elongation ratio lambda, of 1.1, 1.2, 1.3 and 1.5. From the evolution of the dichroic ratio R = A(parallel to)/A(perpendicular to) of v(C-Cl) 615 and 637 cm(-1) frequencies and of relative absorbance A(615)/A(637) in the perpendicular direction, as measured by FTi.r. spectroscopy, it is concluded that stretching causes both the conformational change GTTG(-)TT double right arrow GTGTTT for mmr isotactic tetrads, and the orientation of chains, to be operative, but the relative proportion of both phenomena varies with lambda, the former one being the major effect up to lambda = 1.1. The space charge distribution of all the samples has been studied by coupling the ’thermal step’ (TS) and the ’thermal stimulated discharge current’ (TSDC) techniques. The results, as analysed in the light of earlier work, show that the nature and distribution of the space charges which appear in the film submitted to high electric field, strongly depend on the GTTG(-)TT and GTGTTT conformations of mmr, in particular the former.