The use of nitrite- and nitrate-based inhibitors provides corrosion protection by the development of passive oxide film on the metal surface in reinforced concrete applications. However, the impact of the nitrite and nitrate ratio in the mixture has not been widely studied. In this study, the corrosion protection provided by NaNO2:NaNO3 inhibitor blends with ratios of 0.5:1, 1:1, and 1:0.5 were studied to maximize corrosion inhibition efficiency. The nitrite species imparted higher corrosion protection, as shown by cyclic potentiodynamic polarization, with an icorr of 1.16 × 10–7 A/cm2 for the 1:0.5 mixture, lower than for both the 1:1 and 0.5:1 mixtures. Electrochemical impedance spectroscopy was also performed, with the 1:0.5 mixture consistently displaying high resistance values, showing an Rct of 1.31 × 105 Ω cm2. The effect of temperature was also assessed; the Ea’s of the corrosion reaction were calculated to be 12.1, 9.2, and 4.9 kJ/mol for the 0.5:1, 1:1, and 1:0.5 (NO2−:NO3−) mixtures, respectively. Density functional theory was applied to analyze the molecular properties and to determine the relationship between the quantum properties and corrosion inhibition. The ΔE of NO2− was found to be −5.74 eV, lower than that of NO3− (−5.45 eV), corroborating the experimental results. Lastly, commercially available inhibitor mixtures were investigated and nitrite/nitrate concentrations determined to evaluate their corrosion protection performance; amongst the two inhibitor blends tested, Sika was found to outperform Yara due to its greater NO2− concentration.