To understand whether the optimization of the operating/electrode structural parameters are temperature dependent, a 3D numerical model is developed and validated to gain insight into the impact of practical operating temperature (273.15 K–323.15 K) on vanadium redox flow battery (VRFB) performance, in which the property parameters are from published experimental data. The operating temperature is found significantly influence the optimal design of VRFBs. Increasing the inlet flow rate and state of charge (SOC), decreasing the electrode porosity and fibre diameter can all improve the battery performance with interdigitated flow channels, and the improvement increases with increasing temperature. In contrast, decreasing the fibre diameter or porosity increases the flow resistance and costs higher pump consumption, which is more pronounced at a lower temperature due to higher electrolyte viscosity. The effect of electrode thickness is also different at various temperatures. The gradient porosity electrode is applied in VRFB with interdigitated flow channels. The electrochemical performance of VRFB with gradient electrode (porosity increases from 0.8 at channel side to 0.93 at membrane side) performs similarly with the VRFB with 0.8 porosity electrode, while the pressure drop is reduced by 40% at all temperature. This model provides a deep understanding of effects of a wide range of working temperature on the optimization of operating/electrode parameters and on the VRFBs’ performance.