Abstract Morphological changes resulting from the elongation of poly(tetrafluoroethylene) (PTFE) have been examined using rheo-photoacoustic Fourier transform infra-red (r.p.a. FTi.r.) methodology. Based on the quantitative analysis of the r.p.a. FTi.r. data, several transitions in the film permeability are identified over the range of examined elongations, and the mechanism responsible for these transitions is discussed. Electron microscopy and X-ray diffraction measurements were utilized in an attempt to further support the proposed mechanism of elongation in the negative Poisson ratio region. In contrast to polyethylene and other polymers, this phenomenon is characteristic of PTFE. The strain dichroic ratios obtained using transmission FTi.r. spectroscopy are not sensitive to these transitions.