PEEK was sprayed with a Browning Aerospray HVAF thermal spray gun to enable the study of the wetting and interaction of single splats with an aluminium 5005 substrate. Single splats were obtained by exposing the substrate to the spray flame for 0.02 s by dropping a steel shutter with a 25 mm aperture milled in the centre. The single splats were then analysed through SEM (scanning electron microscopy) and FIB microscopy (focussed ion beam). Splat shape was found to be dependant on nozzle length, with a 100 mm nozzle resulting in more splashing, and a 450 mm spray distance providing more disc splats. PEEK splats do not wet the aluminium oxide surface well. Porosity occurs independently of nozzle length, in the form of cracks and pores in the splats, some cracks completely segmenting a splat.