Atomic force microscopy (AFM) and Fourier transform infra-red spectroscopy (FT i.r.) were used to investigate the nature of poly(ethylene terephthalate) (PET) films formed on the surface of a highly oriented poly(tetrafluoroethylene) (PTFE) substrate mechanically deposited on silicon wafers. PTFE films have been previously shown to be highly effective substrates for the growth of oriented overlayers; such materials often have unique properties. In this study we report FT i.r. observations of an increase in crystallinity of a PET film formed on such an oriented substrate when compared to a film formed on the untreated silicon wafer. AFM imaging is used to show the deeply contrasting surface of the PET film formed on each substrate.