Liquid-liquid extraction studies of tetravalent hafnium from acidic chloride solutions have been carried out with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex 301) as an extractant diluted in kerosene. Increase of acid concentration decreases the percentage extraction of metal. Plot of log D vs. log [HCl] gave a straight line with a negative slope of 2 +/- 0.1 indicating the exchange of two moles of hydrogen ions for every mole of Hf(IV) extractacted into the organic phase. Extraction of Hf(IV) increases with increase of extractant concentration. The plot of log D vs. log [HA] is linear with slope 2 +/- 0.1, indicating the association of two moles of extractant with the extracted metal species. The addition of sodium salts enhanced the percentage extraction of metal, and followed the order NaSCN > Na2SO4 > NaNO3 > NaCl. Stripping of metal from the loaded organic (LO) with HCl and H2SO4 indicated sulphuric acid as the best stripping agent. Increase of temperature increases the percentage extraction of metal indicating the process is endothermic. Regeneration and recycling capacity of Cyanex 301, extraction behavior of associated elements such as Zr(IV), Ti(IV), Al(III), Fe(IH), and IR spectra of the Hf(IV)-Cyanex 301 complex was studied.