The chemical and physical interaction between Fe-Si alloys in the range 0-3.8 Si wt% and a molten Al-(Si 25wt%) alloy at 800 °C has been studied for different reaction times (from 0.1 to 200s) by hot dipping tests. Several intermetallic phases have been identified, Fe2Al5, τ1-Al3Fe3Si2, τ2-Al12Fe6Si5, τ3- Al2FeSi and τ4- Al3FeSi2, which already were reported in the literature dealing with the interaction between iron and molten Al-Si alloys. In addition an ordered phase Fe3Si (D03) appears in contact with the Fe-Si substrate. Diffusion reaction and solidification phenomena appear to be involved in the developing of the coating. The growth kinetic has been studied and diffusion appears as the step controlling the intermetallic compounds growth. Special attention was paid to the effect of the microstructure of the dipped sheet on the interaction with the molten alloy. The higher deformed structures react faster; this effect can be explained by the faster diffusion through high diffusivity paths like grain boundaries and dislocations.