The solvent extraction behavior of vanadium(V) from hydrochloric acid solutions was investigated using tributylphosphate (TBP) in kerosene as an extractant. The results clearly indicate that vanadium(V) is extracted into kerosene as VO2Cl.2HCl.2TBP. The equilibrium constant of the extracted complex was determined. Extraction and stripping isotherms were generated using TBP in kerosene as an extractant with a typical feed solution containing 0.02 mol/dm(3) of vanadium(V) and 5.0 mol/dm(3) of hydrochloric acid. The effect of the nature of the diluent on the extraction of vanadium(V) with TBP was studied and correlated with dielectric constants. The separation and recovery possibilities of vanadium(V) from other associated metal ions, such as magnesium(II), aluminium(III), titanium(IV), chromium(III), manganese(II), and iron (III), present in the waste chloride liquors of titanium minerals processing industry, are discussed.