An electrochemical flow cell with redox-active electrodes was used for selective removal and recovery of vanadium(V) oxyanions from aqueous streams. The cell relies on intrinsic affinity of the redox-active polymer poly(vinyl)ferrocene (PVFc) and demonstrates selectivity of >10 towards vanadium compared to a background electrolyte in 40-fold abundance. We demonstrate highly selective vanadium removal in the presence of various competing anions (i.e., fluoride, bromide, nitrate, and sulfate). Surface elemental analysis reveals significant correlation between PVFc moieties and vanadium-rich regions after adsorption, corroborating the central role of PVFc modulation on vanadium separation. We further propose a vanadium speciation mechanism in which high and low pH environments during adsorption and desorption steps favor formation of, respectively, H2VO3-/ HVO(4)(2-)and H2VO3-/ H3VO4/ VO2+. Results have implications for the development and optimization of flow devices, as per our observations, excessively low pH environments during desorption can lead to subsequent re-adsorption of cationic vanadium(V).