The purpose of this study was to solve the chloride corrosion damage problems of the rebar in reinforced concrete structures under the chloride environment. The effects of 1.0% triethanolamine (abbreviated as 1.0% TEA), 1.0% Ca(NO2)2, and 0.5% TEA + 0.5% Ca(NO2)2 (abbreviated as 1.0% composite corrosion inhibitor) on the electrochemical performance and modification mechanism of the mortar specimens were investigated by combining macro experiment and microanalysis. The results showed that the electrode potential of the rebar was effectively improved by incorporating the 1.0% composite corrosion inhibitor. This composite corrosion inhibitor displayed the ability to stabilize the electrode potential of the rebar; it also formed a passive film on the surfaces of the rebar, protected the rebar from chloride attack, and achieved satisfactory electrochemical performance. In addition, it could also effectively improve the strength of the mortar specimens and possessed the strong ability to bind chloride ions, thus signifying that it could promote cement hydration and accelerate the formation of cement to form AFt crystals. Therefore, the results of this investigation confirmed that this composite corrosion inhibitor could be effectively used in practical engineering to prevent the corrosion of reinforced concrete structures.