The equilibrium of extraction of V(IV) in the V(IV)- SO₄^2- (H⁺, Na⁺)-Cyanex 301 (HA)-kerosene system has been studied. Significant extraction occurs above pH 1 within 10 min. ^CD (extraction ratio at constant pH_(eq) and [HA]_(o,eq)) value is slightly decreased with increasing [V(IV)]_(ini). ^CD is found to be directly proportional to [H⁺]^-n (n ≤ 2), [HA] ² and (1+1.58 [SO₄^2-]). The process is endothermic (DH = 16 kJ/mol). Apparent K_exvalues at 303 K are 10^_-1.419 and 10^_-0.94 in 0.10 and 1.50 mol/L SO₄^2- medium, respectively. The loading capacity is calculated to be7.87 gV(IV) per100 g Cyanex 301. Kerosene appears as the best diluent. Stripping to the extents of 100%, 94% and 97.7% are possible in single stage by 1 mol/L H₂SO₄, HCl and HNO₃, respectively. Separations of V(IV) from Cu(II) (at pH 0), Zn(II) (at pH 0.5) and Fe(III) (at pH 1.0) by Cyanex 301 are possible.