A highly sensitive spectrophotometric method for the determination of 0.03-1.0 μg of arsenic is described. After extraction as AsI3 into benzene, it is selectively stripped into water. Both the arsenic(III) and iodide present in the aqueous phase are made to react with iodate in acidic medium in the presence of chloride to form the anionic chloro complex, ICl-2. The determination is completed after extraction of ICl-2 species as an ion-pair with Rhodamine 6G into benzene and measuring the absorption of the extract at 535 nm. The coefficient of variation is 1.5% for 10 determinations of 0.5 μg of arsenic. The method has been applied to the determination of arsenic content in plant materials, high purity iron, copper base alloys and inorganic arsenic levels of natural waters. © 1992.