Extraction of vanadium(IV) from sulphate acid solution was studied using organophosphorous-based extractants D2EHPA, EHEHPA and CYANEX 272 in kerosene. The different parameters affecting the extraction of vanadium(IV) under equilibrium conditions were separately investigated to elucidate the stoichiometry of the extracted species. The distribution ratio of vanadium increased with increasing equilibrium pH of the aqueous phase, concentration of the extractants and temperature. D2EHPA was found to be a stronger extractant, having greater pH functionality than EHEHPA and CYANEX 272. Extraction of vanadium(IV) by these organophosphorous-based extractants involved cation exchange mechanism, and the extracted species appear to be VOR2(HR)2 in the low equilibrium pH and VOR2 in the higher equilibrium pH, where HR refers to the three acidic extractants.