A sensitive kinetic spectrophotometric method has been developed for the determination of Se(IV) over the range of 45 to 4000 ng in 10 mt of solution. The method is based on the catalytic effect of Se(TV)on the reduction reaction of bromate by hydrazinium dichloride, with subsequent reaction of Ponceau S with products of the above reaction (chlorine and bromine),causing color changing of Ponceau S. Method development includes optimization of time interval for measurement of slope, pH, reagents concentration, and temperature. The optimized conditions yielded a theoretical detection limit of 33 ng/10 mt of solution of Se(IV). The interfering effects were studied and removed. The method was applied to the determination of selenium in spiked water, Kjeldahl tablet, selenium tablet, and shampoo. Vanadium(V) has an inhibition effect on the catalyzed reaction of bromate and hydrazine by selenium. Using this effect, V(V) can be determined in the range of 70 to 2500 ng in 10 mt of solution. The optimization procedure includes pH and selenium concentration. An extraction method was used for interference removal. The method was applied to the determination of vanadium in petroleum.