Mössbauer spectroscopy has been used to investigate the nature of the Zinc-Iron alloys present within the Hot Dip Galvanized (HDG) layers of steel with a silicon content of 0.35%.The investigation also studied the impact of the powder coating pretreatment on the nature of the alloy layers. The acid etching process within the pretreatment process in particular would be expected to have a significant impact on the HDG layer. This study utilized 57 Fe Mössbauer spectroscopy to examine identically processed samples prior to and post pre treatment. XRD and 57 Fe CEMS measurements were performed on hot galvanized S355J2+N samples, forming sandwiched structure. Both XRD and CEMS reveal the presence of dominant steel phase in accordance with its estimated occurrence on the surface of the sandwiched samples. Minor -Fe3Zn10, -FeZn15 and solid solution Fe-Zn as well as minor Fe-Si phases could also be identified.