Polytetrafluoroethylene (PTFE) is one of a class of polymer that has many unique properties, which make it valuable in scores of applications. Here, the molecular alignment effect in fibre drawing and its relation with nonlinear optical properties of the PTFE fibres were studied by means of interferometry. For this propose, the phase shifting Mach-Zehnder interferometer was utilized. The fibre drawing device was attached to the interferometer for measuring the opto-mechanical properties of PTFE fibres. From the recorded interferomgrams the wrapped phase map and its contour line were determined using the phase shifting interferometry (PSI) method. From the contour lines the refractive index, refractive index profile, birefringence, polaryzability and orientation function of the investigated sample were determined at different draw ratios. The PSI method showed good results for enhancing the noisy fringe pattern and for obtaining contour line microinterferograms. This study offers the correlation between the mechanical properties and the structure properties of fibres. Thus, a better structure-property correlation can improve the technical and industry performance of the fibres.