PEEK was sprayed with a Browning Aerospray HVAF thermal spray gun to enable the study of the wetting and interaction of single splats with the aluminium substrate. Single splats were obtained by exposing the substrate to the spray flame for 0.02s by dropping a steel shutter with a 25mm aperture milled in the centre. The single splats were then analysed through SEM (scanning electron microscopy) and FIB microscopy (focussed ion beam). Splats were found to have a decomposed layer on the surface after spraying which was characterised by spatially resolved XPS (x-ray photoelectron spectroscopy). Splat shape was found to be dependant on nozzle length, with a longer nozzle resulting in more splashing. PEEK splats do not wet the aluminium oxide surface and significant porosity occurs between the substrate and the splat, whilst porosity in the splats is proportional to the length of nozzle.