The effects of phenols as additives on the solvent extraction of titanium(IV) with acetylacetone in carbon tetrachloride have been investigated. Titanium(IV) is scarcely extracted with acetylacetone, and the extractability is lower than that of the other titanium group metals, zirconium(IV) and hafnium(IV). However, the extractability of titanium(IV) acety lacetonate is greatly enhanced in the presence of 3,5-dichlorophenol where titanium(IV) can be extracted quantitatively and better than zirconium(IV) or hafnium(IV). The effects of the phenols (3,5-dichlorophenol, 3,5-dimethylphenol, and 4-chlorophenol) are greater than that of benzoic acid, and the phenol with the lower pKavalue is more effective. From equilibrium analy sis on the extraction system using 3,5-dichlorophenol (Hdcp), it was found that one mole of titanium(IV) is extracted together with two moles of acetylacetone (Hacac) and one to three moles of the phenol; one of the extracted species is suggested to be Ti(acac)2(dcp)2Hdcp.