The corrosion has a detrimental effect on the reinforced concrete structure. Hot-dip galvanized (GS) offers more resistance against corrosion because the zinc-coated layer plays a role as a sacrificial anode when compared to conventional steel. The use of GS may help increase reinforced concrete structure’s service life in which chloride-induced corrosion is the main deterioration. The initial corrosion, or passivation of GS is important to ensure the protection of galvanized reinforced concrete. Unlike conventional steel, the passivation of the galvanized steel is instead generated by a vigorous reaction between the galvanized coating and fresh concrete that results in a protective layer of calcium hydroxyzine (CHZ). This process is also involved by hydrogen evolution. Therefore, pores at the steel-concrete interface between concrete and GS may increase due to the formation of gaseous hydrogen, which may further affect the bonding performance of the GS reinforcing steel. A comparative study on bond strength and open circuit potential (OCP) of GS and bare steel (BS) was conducted. Both GS and BS were embedded in different mix proportions of concrete with different binder systems, water-to-binder ratio (w/b), and initial chloride content. The OCP of GS at the early hours of fresh concrete dropped below −1.07 V versus CSE which showed the evidence of hydrogen evolution. The OCP value shifted to a higher value after the vigorous reaction that formed the protective layer of CHZ on the surface of GS. According to the formation of the gaseous hydrogen, the contact area between steel and concrete was reduced, thereby decreasing the bond strength compared to bare steel.