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Vanadium(V) is an emerging contaminant in the most recent Environmental Protection Agency’s candidate contaminant list (CCL4). The redox chemistry of vanadium controls its occurrence in the aquatic environment, but the impact of vanadium(V) speciation on the redox properties remains largely unknown. This study utilized the rotating ring-disk electrode technique to examine the reduction kinetics of four pH- and concentration-dependent vanadium(V) species in the presence and the absence of phosphate. Results showed that the reduction of VO2+, HxV4O12+x(4+x)–(V4), and HVO42–proceeded via a one-electron transfer, while that of NaxHyV10O28(6–x–y)–(V10) underwent a two-electron transfer. Koutecky–Levich and Tafel analyses showed that the intrinsic reduction rate constants followed the order of V10> VO2+> V4> HVO42–. Ring-electrode collection efficiency indicated that the reduction product of V10was stable, while those of VO2+, HVO42–, and V4had short half-lives that ranged from milliseconds to seconds. With molar ratios of phosphate to vanadium(V) varying from 0 to 1, phosphate accelerated the reduction kinetics of V10and V4and enhanced the stability of the reduction products of VO2+, V4, and HVO42–. This study suggests that phosphate complexation could enhance the reductive removal of vanadium(V) and inhibit the reoxidation of its reduction product in water treatment.