Coatings of poly(ether-ether-ketone) (PEEK) have been produced using the high-velocity air fuel (HVAF) thermal spray technique. These coatings have been produced at 50 and 100 mm nozzle lengths and 200, 300, and 400 mm gun-to-substrate distances on stainless steel 304 substrates. The techniques used to characterize and determine the extent of thermal degradation of the PEEK coatings were valence-band XPS and FTIR-ATR. Valence-band XPS showed that, in general, minimal degradation of the PEEK occurred during the HVAF thermal spraying process. FTIR-ATR results showed that more surface degradation of the PEEK coating occurred at the 200 mm gun-to-substrate distance for both nozzle lengths than at the larger gun-to-substrate distances. Specifically, absorption bands appeared at 2918 and 2850 cm-1, which correspond to alkane –CH2– asymmetric stretching modes. The resolution of the 672 cm-1 peak, which corresponds to C–H vibrations on the phenyl ring, increased from one to two peaks in the spectra of the 200 and 300 mm gun-to-substrate runs. This indicates a structural change in the phenyl ring, possibly indicating a change in the extent of crystallization of the PEEK polymer.