Corrosion is known as a breakdown effect that causes the deterioration of substances in enriched petroleum/gas conditions. This reaction occurs in all materials, which is highlighted in alloys. In the present study, the morphological properties, as well as the corrosion resistance behavior of the AISI1045 steel substrate coated with 321 austenitic stainless steel metal particulate fillers, were investigated. The electro-explosive spraying technique was employed to achieve a homogenous coating on the substrate surface. According to the results, the grain size of the 321 austenitic stainless steel coating layer was shrunk and reduced to 1–3 μm after the coating procedure. The coated layer also showed a homogenous and uniform thickness with an average value of 137 μm. Also, the average adhesion strength of 49.21 MPa was obtained between the sprayed coating and the substrate. The analytical analysis found the presence of Fe-Cr and Fe-Ni phases in the coating layer. The hardness of the original metal wire is 186 HV, and the microhardness of the coating after spraying is 232 HV. After subjecting the specimen to the corrosion examination, a 0.1961 mm/a corrosion rate was obtained for up to 120 h. Moreover, the corrosion products of CaCO3, Fe3O4, and MgFe2O4 were determined by XRD analysis. Furthermore, the observed results were further confirmed by the data obtained from EPMA and EDS evaluations. Hence, this study implies the beneficial role of electro-explosive sprayed alloy 321 austenitic stainless steel in creating a protective layer against corrosion on 45 steel substrate in an enriched oil/water environment.