The purpose of this paper is to develop an equivalent-circuit model (ECM) of a vanadium redox flow battery (VRFB)-based energy-storage system (ESS) for simulating its operating characteristics under distinct charging and discharging conditions. Comparative experimental measured results and computer simulated outcomes of a VRFB-ESS subject to various charging and discharging conditions are demonstrated in this paper. The laboratory experimental platform of the studied VRFB-ESS includes an experimental VRFB set of rated 500 W, a battery monitoring instrument, a programmable DC power supply, a single-phase DC/AC power inverter, an AC load, and a power-resistor load. The parameters of the ECM of the studied VRFB-ESS are obtained from some selected measured results. After comparing the measured and simulated results, the average errors of voltage and power of the studied VRFB-ESS under distinct charging and discharging operations can be less than the expected tolerance of 2%.