Two contrasting infrared spectroscopic techniques, Attenuated Total Reflectance (ATR) and PhotoAcoustic Spectroscopy (PAS), have been investigated as means for the determination of fluorocarbon polymer finishes on wool fabric. Based on the experimental conditions used, the results of the PAS method are more characteristic of the bulk sample, while the ATR results are more surface specific. Linear calibrations between polymer add-on, as determined by total fluorine analysis, and the absorbance of the C-F stretching bands of the normalized spectral data were obtained for a typical commercial fluorocarbon polymer. The correlation obtained for the PAS method was found to be significantly better than that of the ATR method. The lower limit of detection of fluorocarbon polymers on wool using the PAS technique was 0.25% on the weight of the wool (oww). In contrast, fluorocarbon polymer add-ons as low as 0.125% oww (approximating monolayer coverage) could be analyzed using the ATR method. At high levels of add-on, the ATR calibration deviated from linearity. This can be attributed to the distribution of fluorocarbon polymer on the surface of the fiber, in particular, the build up of polymer on the cuticle cell edge regions. The quantitative methods developed are used to help access the effects of wear and the subsequent heating of fluorocarbon polymer-treated fabric samples.