The progress of textile recycling is significantly impeded by the absence of adequate methodologies for determining the composition of fibres in textile blends. The examination of textile mixtures poses considerable difficulties, particularly due to the presence of elastane fibres, which in their limited quantities cannot be easily detected using conventional analytical techniques. Further, the undetected elastane fibres pose difficulty in separation during recycling of the textiles as they end up as impurities in cases where dissolution of the fibres is employed. Consequently, it is of utmost importance to explore new analytical tools that possess the capability to identify the primary fibres in post-consumer waste. In the current investigation, we conducted a study to assess the capabilities of Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Pyrolysis coupled with Gas Chromatography and Mass Spectrometry (Py-GC/MS) for the characterization of postconsumer textile fabrics. A comprehensive pyrolysis database was established encompassing prevalent pure fibres commonly employed in textile production. In addition, an examination was conducted on three textile blends with predetermined compositions, and the findings were subsequently compared with data obtained through the utilization of ATR-FTIR. The data derived from the original fibres was ultimately utilized for the examination of post-consumer fabric samples acquired from a waste landfill. The utilization of Py-GC/MS, scanning electron microscopy (SEM) and ATR-FTIR enabled to discern fibre compositions of mixtures even those that contained relatively low fibre content.