[en] A highly sensitive, selective and rapid solvent extraction procedure for spectrophotometric method of determination of sub trace amount of vanadium(V) in methyl isobutyl ketone has been reported in this paper. Vanadium(V) is extracted with N-cinnamohydroxamic acid (N-CHA) and a mixed ligand thiocyanate (SCN) as a violet coloured complex in solvent phase at 1.8 M HCl. The ternary complex absorbs maximum at 555 nm. The system obeyed Beer's law from 0.4 to 12 ppm with optimum range of determination 1-9 ppm of V(V). The molar absorptivity and Sandell's sensitivity are 0.745 x 10⁴ 1.mole^-1 cm^-1 and 6.8 ng cm^-2 of V(V) at 555 nm. A large number of cations and anions do not interfere. The method shows high selectivity with thiouriede as masking agent and it is simple, rapid, reproducible and reports high precision. The R.S.D. value is ± 0.0012 for average of seven determinations. The photometric determinations are also reported in detail and the standard deviations are minimal. The R.S.D. values are different for the steel (0.08%), rock (2-3%) and ore (2%) samples. (author)