Single NiCr splats were plasma-sprayed onto a polished stainless steel substrate held at room temperature. The splat-substrate interface was characterized by focused ion beam and transmission electron microscopy. The frequent observation of NiO particles, particularly in pores within the splat, and at the periphery of splat, suggests that the principal oxidation process occurs at the substrate surface, where the splats are exposed to a water vapor-rich environment. It was also observed that the splat adhered well in some locations where elemental-diffusion and jetting of the substrate occurred, suggestive of substrate melting. A three-dimensional numerical model was developed to simulate the impact of a splat onto a substrate. The simulation shows that the observation of the central pore in the splat and the phenomenon of substrate melting may occur. Based on these results, the effect of water release on oxide formation and splat morphology can be explained.