The electrochemical behavior of the Fe(III)/Fe(II)–triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)–TEA can be increased to 0.6M, and the solubility of the Fe(II)–TEA is up to 0.4M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)–TEA complex at low scan rate can be minimized. The electrode process of Fe(III)–TEA/Fe(II)–TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge–discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe–TEA/Br2 cell with the Fe(III)–TEA of 0.4M, after full charging, is nearly 2.0V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)–TEA/Fe(II)–TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application.