Ni-Cr single splats were plasma-sprayed at room temperature onto aluminum and stainless steel substrates, which were modified by thermal and hydrothermal treatments to control the oxide surface chemistry. The proportions of the different splat types were found to vary as a function of substrate pretreatment, especially when the pretreatment involved heating. It was observed that surface roughness did not correlate with changes in splat morphology. Substrate surfaces were characterized by X-ray photoelectron spectroscopy using in situ heating in vacuum to determine the effect of thermal pretreatment on substrate surface chemistry. It was found that the surface layers were composed primarily of oxyhydroxides. When the substrates were heated to 350°C, water vapor was released from the dehydration of oxyhydroxide. Preheating the substrate can remove the water prior to spraying: preheated substrates had improved the physical contact between the splat and substrate, which enhanced the formation of disk splats and increased the number of splats.