1-(2-Hydroxy-4-methoxybenzophenone)-4-phenylthiosemicarbazone (HMBPT) was investigated as a new reagent for the flotation of vanadium(IV). At pH ∼1.5, vanadium(IV) forms a 1:1 pale-violet complex with HMBPT in aqueous solution. An intense clear violet layer was formed after flotation, by adding an oleic acid (HOL) surfactant. The composition of the float was 1:1 [V(IV)]: [HMBPT]. A highly selective and sensitive spectrophotometric procedure was proposed for the determination of microamounts of V(IV) as its floated complex. The molar absorptivities of the V(IV)-HMBPT and V(IV)-HMBPT-HOL systems were 0.4 × 10 4 and 0.12 × 10 5 L mol -1 cm -1 at 560 nm, respectively. The formation constants of the species formed in the presence and absence of HOL were 4.6 × 10 7 and 8.7 × 10 5 L mol -1 , respectively. Beer's law was obeyed up to 1 × 10 -4 mol L -1 in the aqueous layer as well as in the oleic acid layer. The HMBPT-V(IV) complexes formed in the aqueous solution and scum layer were characterized by elemental analysis, infrared and UV spectrophotometric studies. The mode of chelation between V(IV) and HMBPT is proposed to be due to a reaction between the protonated bidentate HMBPT ligand and V(IV) through the S=C and N=C groups. Interferences from various foreign ions were avoided by adding excess HMBPT and/or Na2S2O3 as a masking agent. The proposed flotation 1 method was successfully applied to the analysis of V(IV) in synthetic mixtures, wastes of power stations, simulated samples and in real ores. The separation mechanism is discussed.