Vanadium is an important scarce resource and strategic metal, and often coexists with a variety of complex metals in the form of secondary mineral phases in nature. The effect of co-exist elements on the selection of spectral lines in the determination of vanadium with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-OES) was studied in this article. The selected PE Optima 7300V instrument was operated under the conditions of incident power 1 300 W, observation height 15 mm and atomization gas flow rate 0.65 L·min-1. The results show that Al, Mo, Ti, Cr and Ni have significant effects on the determination of vanadium under six recommended spectral lines, and the relationship between the relative error of measurement results and the mass ratio of the corresponding element to V waslinear. The presence of trace Al leads to drastic changes when V 309.31 nm spectral lines was adopted. The relative error of V 290.88 and V 292.402 nm spectral lines were increased to more than ±5% as the Mo/V mass ratio increased to 0.89 and 5.98, separately. The Mo measurement results were unstable when V 270.093 nm spectral lines was adopted, but nothing regular. The relative error of V 311.07, 290.88, 270.093 and 310.23 nm spectral lines were increased to more than ±5% as the Ti/V mass ratio increased to 5.98, Cr/V mass ratio increased to 10.33, 13.6, and Ni/V mass ratio increased to 13.56, respectively. Considering the above effects and spectral stability, V 311.07 nm spectral lines can be adopted when there has no titanium in vanadium-containing raw materials, and V 310.23 nm can be used when there has titanium contained. Under the optimum analytical conditions of the spectrometer, the method was used for the determination of vanadium in typical vanadium-containing raw materials such as vanadium-titanium magnetite, stone coal and vanadium-containing catalysts with the detection limit of 0.054 mg·L-1 at 310.23 nm, 0.194 mg·L-1 at 311.07 nm, recoveries between 93.4% and 103.1%, and relative standard deviation of 0.59%. By comparing with the results of ammonium ferrous sulfate titration method, the results were basically consistent with the relative error of less than ±4.34%. In conclusion, the method was simple and efficient, with high precision and accuracy, which can be used for research and routine production of vanadium determination in raw materials containing vanadium.