A protective coating was built and assessed in order to reduce the degradation of metallic substrates caused by corrosion damage. Hence, a set of coatings with different configurations, in terms of layer arrangement, was produced by flame-spraying of composite powder (AISI 316L stainless steel coated with an α-alumina layer) onto an AISI 1018 steel substrate. In order to ensure a homogeneous dispersion of phases, a correlation was established between the operating parameters of thermal spraying (roughness and surface temperature of substrate, spraying distance, passing speed) and the splat formation. Then, corrosion damage caused in the coated samples by exposure to a salt spray was monitored through weight measurements and observations with optical and scanning electron microscopy. The results show that corrosion still remains in all cases; however, it proceeds at lower rates for coatings made with composite particles plus an α-alumina layer. The weight loss due to corrosion damage was reduced in approximately 94% as compared with the substrate without protection. Coating adhesion was also improved by an increased substrate roughness, with no need for an intermediate layer.