A series of samples are collected from the catholyte solution of a vanadium redox flow battery (VRFB) at different values of state of charge (SoC)/state of discharge (SoD). The samples are analyzed by means of Raman spectroscopy to identify: (i) the species present into the catholyte; and (ii) how the composition of the catholyte is modulated along the charge and discharge processes of the VRFB. Raman results reveal that the most abundant species in the catholye are VO2+ and VO2 +; they are coordinated by HSO4 − and SO4 2− ligands. During the charge process of the VRFB the equilibrium between the vanadium species is shifted towards the formation of an ensemble of V(V) complexes. Instead, during discharge a family of V(IV) species is obtained. The formation of concatenated HV2O5 − and H3V2O7 − species in the catholyte is revealed, which indicates that side electrochemical reactions occur during the charge and discharge processes of a VRFB. The presence of these side reactions plays a crucial role in the modulation of the Coulombic efficiency of the VRFB. This work highlights the complexity of the chemical situation at a VRFB cathode, and the great importance to understand/control such chemical situation to improve the performance of VRFBs in the scenario of electrochemical energy storage field.