The performance of a unitised bidirectional vanadium/air redox flow battery (VARFB) is described. It contains a two-layered cathode consisting of a gas diffusion electrode (GDE) with Pt/C catalyst for discharging and of an IrO2 modified graphite felt for charging. A simple routine is shown for the modification of a graphite felt with IrO2. A maximum energy efficiency of 41.7% at a current density of 20 mA cm−2 as well as an average discharge power density of 34.6 mW cm−2 at 40 mA cm−2 were obtained for VARFB operation at room temperature with the novel cathode setup. A dynamic hydrogen electrode was used to monitor half cell potentials during operation allowing to quantify the contribution of the cathode to the overall performance of the VARFB. Four consecutive cycles revealed that crossover of vanadium ions took place and irreversible degradation processes within the reaction unit lead to a performance decrease.