Reactive MgO cement (RMC) has an ability to gain strength by carbonation. One of the main concerns in RMC systems is the potential corrosion of reinforcing steel in structural applications. This study evaluated the feasibility of replacing small proportions of RMC with Portland cement (PC) to promote the passivation of reinforcing steel. Reinforcing steels embedded in RMC with different proportions of PC were investigated by electrochemical measurements and microstructural analysis. Pore solutions extracted from these pastes were evaluated for their chemical compositions. Inclusion of ≥2% PC enabled the passivation of steel. Passive film forming in RMC-PC blends consisted of Fe3O4 and Mg(OH)2, which was thicker than those in pure PC mixes. The formation of passive film was mainly attributed to the increased pH of the pore solution, which reached over 12 in RMC mixes containing only 2% PC. These findings highlighted the potential of using RMC mixes in reinforced concrete applications.