The effect of chromium substrate preheating on the spreading behavior of plasma-sprayed nickel splats was characterized. The interfacial features along the splat-substrate interface were analyzed by focused ion beam (FIB) microscopy and transmission electron microscopy (TEM). In addition, the transient droplet spreading process was modelled in a simulation study. The results showed that the presence of a large fraction of surface moisture on the substrates induced splat fragmentation. However, splat fragmentation was completely constrained on chromium preheated to a low temperature (373 K) where a certain amount of surface moisture was still present. The high thermal conductivity of chromium substrates increased droplet solidification rates, decreasing the interaction time between the spreading droplet and the vaporized gas layer. Accordingly, splat fragmentation was suppressed and disk-shaped splats were formed. Fast solidification not only refined the final splat microstructure, but also promoted the formation of finger-splashed disk splats. In addition, the extent of elemental diffusion across the splat-substrate interface was decreased due to the low interfacial temperature.