In order to develop a quick, efficient and sensitive valence analysis method of vanadium(V), the high- performance liquid chromatography (HPLC) was utilized to separate and quantify EDTA-complexed V(III), V(IV) and V(V) ions. The influence of EDTA, TBAOH, solution pH and organic modifier on retention behavior of V-EDTA complexes was investigated. Complexed V(III), V(IV) and V(V) ions can be separated and quantified in 5 min, with detection limits of 0.04 mg/L V(III), 0.07 mg/L V(IV), and 0.06 mg/L V(V), respectively. The established method is applied to analyzing the hazardous waste of V-Cr-bearing reducing slag and results demonstrate 49.94% of its V element to be toxic V(V). This work opens a new avenue for quick and accurate toxicity assessment of hazardous wastes containing multivalent heavy metals.