Silicate conversion coating is considered as an alternative to hexavalent chromium conversion coating for corrosion protection of galvanized steels. However, the coating must be treated with hot air afterward in order to obtain a water resistant silicate layer and to increase corrosion resistance of the coating. Moreover, it is difficult to apply the uniform thermal treatments on the large irregular shaped metal parts. Furthermore, the heat treatment is an energy consuming process. In this work, the effects of adding potassium methyl siliconate (PMS) into the silicate conversion coating on the anti-corrosion properties were studied. The silicate coating layers were formed by the simple immersion into the silicate solutions and the subsequent ambient drying at room temperature. It was verified that the addition of potassium methyl siliconate increased the temporary corrosion protection ability without the post-thermal treatments. Coating thickness was around 100 nm and K ion was distributed preferentially at zinc-silicate interface. It was proved that the more hydrophobic surface was formed mainly due to the substantial decrease of the concentration of K ion at the coating surface by the addition of Potassium methyl Siliconate . It was a methyl group of PMS that changed the hydrophilic silicate layers into hydrophobic ones. Subsequently, the enhanced water barrier property of the hydrophobic silicate layers increased the corrosion resistance of the silicate-coated galvanized steel.