Organic-inorganic hybrid (OIH) matrices were synthesized by sol-gel method and deposited on hot-dip galvanized steel (HDGS) using a dip-coating process. These OIHs, generally called amino-alcohol-silicates, were synthesized using a functionalized siloxane, 3-glycidoxypropyltrimethoxysilane, and five oligopolymers (Jeffamine) with different molecular weights: 230, 400, 600, 900 and 2000. Besides the five different pure OIH matrix coatings, a similar set of HDGS samples were coated with the OIH matrices doped with Cr(III), which was tested as a corrosion inhibitor. The OIH coatings were assessed using electrochemical studies, namely electrochemical impedance spectroscopy, macrocell current density, open circuit potential monitoring and polarization resistance. The studies were carried out in mortar. Analysis of the results obtained by optical and scanning electronic microscopy methods were consistent with the data obtained by electrochemical techniques. The HDGS samples coated with OIH matrices showed better performance when compared with HDGS uncoated samples. ; Funda????o para a Ci??ncia e a Tecnologia (FCT)