The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.