Two methods for the determination of pyrithioxine in pharmaceutical formulations by means of oxidative coupling and extractive spectrophotometry are described. Oxidative coupling of pyrithioxine (PYT) with 3-methyl -2- benzothiazolinone hydrazone hydrochloride (MBTH) in the presence of cerium ammonium sulphate (Ce(IV)) forms a coloured product (Method A). The coloured product has maximum absorbance at 635 nm. The second method is based on the formation of an ion-association complex of pyrithioxine with suprachen violet 3B (SV3B) at pH 1.3 which is extracted into chloroform (Method B). The complex has maximum absorbance at 550 nm. The methods obey Beer's law and the precision and accuracy of the methods are checked by U.V. reference method9. These methods have been applied to the determination of pyrithioxine in pharmaceutical formulations.