The composition, stability constants and molar absorption coefficients of the chelates of thulium, ytterbium, lutetium and thorium ions with Semi-xylenol Orange (SXO) are determined spectrophotometrically in a medium of hexamine, and chloroacetate buffer. In the thulium, ytterbium, lutetium and thorium-Semi-xylenol Orange systems, Tm(SXO), Yb(SXO), Lu(SXO) and Th(SXO) chelates are formed with logarithmic overall stability constants of 12.48+/-0.01, 12.55+/-0.01, 12.94+/-0.015 and 22.16+/-0.01 and molar absorption coefficients of 2.22x10(4) (530 nm), 2.17x10(4) (532 nm), 2.25x10(4) (530 nm) and 3.33x10(4) (535 nm) dm3 mol-1 cm-1 respectively. The precision and accuracy attainable in direct spectrophotometric titrations of the Tm3+, Yb3+, Lu3+ and Th4+ separately and the successive determination of each of the three rare earths and Th4+ ion with a 0.001 mol dm-3 solutions of diethylenetriaminepentaacetic acid (DTPA) and PbCl2 of the same concentration using Semi-xylenol Orange (SXO) as a metallochromic indicator have been studied. Thorium (IV) is initially titrated directly at pH 2 (535 nm). At the thorium end-point the pH is adjusted to 5.6-5.8 by adding hexamethylenetetramine (hexamine) buffer and an excess of DTPA is added and Tm3+ (or Yb3+ or Lu3+) is determined by back-titration with standard PbCl2 solution (490 nm). Interferences of different anions, cations and organic acids on the spectrophotometric micro-titration of Th4+ and Tm3+ Yb3+ and Lu3+ are also investigated. Spectrophotometric determination of Tm3+, Yb3+, LU3+ and Th4+ individually using SXO at the optimum conditions of maximum colour development have been carried out. Thorium has been determined spectrophotoMetrically in three different artificial samples with lutetium Similar to those of monazite mineral. Ytterbium (III) has been determined in three different laboratory synthesized samples with Ca2+ and Fe3+ similar to those of euxenite mineral which occurs in nature and the results were reproducible and satisfactory.