Abstract: Vanadium in vanadium-titanium magnetite samples was determined by micro digestion-spectrophotometry with 5-bromo PADAP hydrogen peroxide system. The experimental conditions for microwave digestion were optimized. The interference from coexistent major elements of iron and titanium was studied and eliminated by using concentrated H₃PO₄ and 40 g/L NaF. The detection limit of the method for vanadium was 0.004 μg/mL with linear range of 0.01~1.0 μg/mL. The method had been applied to the determination of vanadium in vanadium-titanium magnetite samples with satisfactory results. The method provides the advantages of low detection limit, good reproducibility, high sensitivity, high efficiency, simple operation and suitable for the routine sample analysis.