Abstract: The accurate determination of vanadium（V）, chromium（Cr） and arsenic（As） contents in aluminum and aluminum alloys is of great significance for the production and application of aluminum and aluminum alloys. When the silicon content（mass fraction, the same below） in aluminum and aluminum alloys was less than 0.5%, the sample was dissolved with mixed acid(V_HCl∶■∶■=10∶1∶10). When the silicon content was not less than 0.5%, the sample was dissolved with 200 g/L sodium hydroxide solution followed by acidification with mixed acid. In the tandem quadrupole（MS/MS） mode, the mass-to-charge ratio（m/z） of the primary mass filter（Q1） was set to 51, 52, and 75. Then, NH₃ and O₂ were successively introduced into the collision/reaction cell. ³⁵Cl¹⁶O⁺ reacted with NH₃ through redox reaction to form polyatomic ions with m/z values not equal to 51. ⁵²Cr⁺ and ⁷⁵As⁺ reacted with O₂ to form ⁵²Cr¹⁶O⁺ and ⁷⁵As¹⁶O⁺, respectively. The interfering ions ³⁵Cl¹⁶OH⁺ and ⁴⁰Ar³⁵Cl⁺ could not react with O₂. Therefore, the m/z of the second mass filter（Q2） were set to 51, 68, and 91. Only ⁵¹V⁺, ⁵²Cr¹⁶O⁺, and ⁷⁵As¹⁶O⁺ passed through and were detected by the detector, thereby avoiding the mass spectrometric interference of ³⁵Cl¹⁶O⁺,³⁵Cl¹⁶OH⁺, and ⁴⁰Ar³⁵Cl⁺. Accordingly, the method for the determination of V, Cr and As in aluminum and aluminum alloys by inductively coupled plasma tandem mass spectrometry（ICP-MS/MS） was established. The flow rates of NH₃ and O₂ were optimized: the flow rate of NH₃ was set at 0.40 mL/min and the flow rate of O₂ were selected at 1.20 mL/min. The linear relationship was good for the mass concentration in range of 0.25-50.00 ng/mL, and the correlation coefficients were higher than 0.999 5. When the sample was dissolved with mixed acid, the limits of detection for testing elements were 0.024-0.12 μg/g, and the limits of quantification were 0.080-0.39 μg/g. When the sample was dissolved with 200 g/L sodium hydroxide solution, the limits of detection for testing elements were 0.064-0.17 μg/g, and the limits of quantification were 0.22-0.56 μg/g. The aluminum alloy standard sample was determined according to the experimental method, and the found results were basically consistent with the certified values. The contents of V, Cr and As in aluminum and aluminum alloys with different silicon contents were determined. The relative standard deviations（RSD, n=11） of determination results were between 1.4% and 9.4%, and the spiked recoveries were between 95% and 115%.