This paper embodies details on the extraction behavior of Ti(TV) along with Mg(II), Mn(II), Fe(III), Al(III), Ce(IV), and V(V) from hydrochloric acid medium employing mono- and di-sulphur analogues of bis-(2,4,4-trimethylpentyl) phosphinic acid, namely bis-(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302) and bis-(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301). The effect of various parameters, such as the concentration of the acid, metal ion, and extractant, and the nature of the diluent on the extraction of Ti(TV) has been investigated. Almost quantitative extraction of Ti(TV) is observed in both the extractants in the 1x10(-2) to 0.5 M acidity range. The extractants can hold the metal ion up to one-tenth of its molar concentration. The extracting species is proposed to be Ti(OH)(2) R-2, (HR = Cyanex 301/Cyanex 302). The partition data have been utilized for obtaining some binary separations of Ti(IV) from some commonly associated metal ions. The practical utility of the extractant has been demonstrated by recovering Ti(IV) from ilmenite and red mud.