A two-dimensional quasi-steady-state model is presented to simulate coupled mass-species-charge transfer and electrochemical reactions in all vanadium redox flow battery. Emphasis is located on examining the influences of applied current density, initial vanadium concentration, initial acid concentration and electrolyte flow rate on overpotentials in both electrodes, ohmic loss in electrolyte phase as well as battery discharging voltage. It is indicated that overpotential in negative electrode is the dominant factor causing the loss of battery discharging voltage at relatively lower or higher state of charge, while ohmic loss in electrolyte phase is dominant when discharging at moderate state of charge. Increasing initial vanadium concentration, the battery discharging voltage is significantly increased due to the reduced overpotentials in both electrodes. With the increase in initial acid concentration, the battery discharging voltage is also obviously increased because of increased open circuit voltage and decreased ohmic loss in electrolyte phase. As the electrolyte flow rate increases, the total discharging time is extended due to the retarded concentration polarization and the battery discharging voltage is obviously increased at lower state of charge.