A 0-D dynamic mathematical model for a single Vanadium Redox Flow Battery (VRFB) cell is proposed. The model is based on the conservation principles of charge and mass transfer focusing on the precise simulation of crossover with diffusion, migration and convection. The influence of these phenomena on the capacity decay was systematically analyzed, revealing considerable impact of convection component, which dominates under diffusion and migration and mainly responsible for observed capacity loss. The model allows to simulate main characteristics of VRFB systems (such as battery voltage, state of charge, charge/discharge time and capacity decay due to crossover) with high accuracy. The model was validated with experimental data in the wide range of current densities (40–100 mA cm−2), and the results demonstrated good agreement with experiments having an average error within 5% range. In addition, the model requires a modest computational time and power, and, therefore, it can be suitable for application in advanced control-monitoring tools, which are necessary for a long-service life and sustainable operation of VRFB systems.