A simple, rapid, sensitive and highly selective method for extraction-photometric determination of microamounts of vanadium(V) is described. The method is based on the formation of the VO(OAm)2-OH complex by the reaction of vanadium(V) withN-hydroxy-N-p-chlorophenyl-N'-(3-chloro-4-methylphenyl)-p-toluamidine, and its extraction into chloroform as 1∶1 adducts [VO(OAm)2OH∶L] (where HOAm=theN-hydroxyamidine and L=carboxylic acid) with various carboxylic acids. The nature of carboxylic acids has large effect in theλmax andɛ of ternary complexes. The sequestrating agents e. g. oxalic, succinic, fumaric, citric, tartraric acid have been also used as a Synergist in the extraction of vanadium(V). Apparent molar absorptivities of the extracts lie in the range of 3100–6700 l · mole−1 · cm−1. Fe3+, Cu2+, Zn2+, Co2+, Ni2+, Cr3+, Mn2+, Ti4+, Zr4+, Mo6+ and W6+ do not interfere. The method has been applied to various alloys.