Polypropylene (PP) was flame sprayed onto rough mild steel substrates at room temperature (RT) that was preheated at 70 °C, 120 °C, and 170 °C. Single solidified droplets (splats) were collected and analysed to understand how processing variables influenced the thermal spray coating characteristics. The splat morphology was characterized in detail using optical and scanning electron microscopy (SEM). The splats exhibited a disk-like shape with a large central viscous core and a fully melted wide rim with a thin edge. The splat size increased with increasing substrate temperature. A unique flat microstructure was observed on the surface of the splat deposited onto the RT substrate, whereas a flowing pattern appeared on the splat surfaces deposited onto the preheated substrates and the pattern increased by increasing the substrate temperature. The results of this study revealed improved splat-substrate adhesion by heating the substrate from RT to 170 °C. On the basis of the result, the influence of substrate parameters on splat morphologies was employed to establish a relationship between the microstructural characteristics and processing variables of flame sprayed polymeric coatings.