The chromogenic reaction of the O-hydroxybenzenediazoaminoazobenzene (O-HDAA) with thallium was studied in this paper. In the presence of Triton X-100 and SDBS and in ammonia medium of 0.54-1.1 mol.L-1, O-HDAA reacts with thallium (III) to form a stable red complex with molar radio of 1:5. The apparent molar absorptivity is 1.4 x 10(5) L.mol-1.cm-1 at the maximum absorption wavelength of 520 nm. Beer's law is obeyed in the concentration range of 0-600 micrograms.L-1 Tl(III). The method has been applied to the direct determination of trace amounts of thallium in waste water and in geological samples by using polyurethane foam to absorb and separate Tl(III) with satisfactory results.