Mullite's inherent qualities have made it a potential material for the application of thermal barrier coatings (TBCs) for diesel engine components. Hot corrosion at 600–800 °C can cause TBC degradation, thus significantly affecting the performance of engine components and reducing their service life. This work examines the hot corrosion behaviour of atmospheric plasma-sprayed (APS) mullite coating over NiCrAlY bond coat on mild steel substrates. The coated specimen surface was covered with a mixture of Na2SO4 (sodium sulphate) and V2O5 (vanadium pentoxide) in the form of paste and heated in a muffle furnace at 700 °C for up to 300 h. SEM, EDS, and XRD characterisations were used to investigate the mechanism of hot corrosion. Coatings remained intact after corrosion tests; however, it had reacted with corrosive salts, particularly sodium sulphate. This was evidenced by the removal of amorphous silica, followed by the formation of nosean as a major phase. During the reaction between sodium sulphate and mullite coating, vanadium pentoxide was found to be acting as a flux and mineraliser.