Coating efficiency and quality can be significantly improved by carefully optimizing the coating parameters. Particularly in the flame spray method, the oxygen/fuel ratio, which is classified as oxidizing flame stoichiometry (excess oxygen) and reduces flame stoichiometry (excess acetylene), and spray distance are the most critical factors, as they correlate significantly with coating porosity and corrosion performance. Hence, understanding the effects of these parameters is essential to further minimize the porosity, improving the corrosion performance of thermally sprayed coatings. In this work, a NiWCrBSi alloy coating was deposited via the oxyacetylene flame spray/Flexicord-wire (FS/FC) method. The effect of the flame oxygen/fuel ratio and spray distance on the microstructure properties and corrosion behavior of the coatings was investigated. Afterwards, the microstructure, phases’ compositions, spray distance, and corrosion performance were studied. The equivalent circuit model was proposed, and the corrosion mechanism was discussed. The obtained results highlight that the oxygen-to-fuel ratio is a promising solution for the further application of flame spray/Flexicord-wire (FS/FC) cermet coatings in hostile environments. Depending on the flame’s oxygen/fuel ratio, careful selection of the flame stoichiometry provides low porosity and high corrosion performance.