The sodium metavanadate samples are digested in hydrochloric acid, and the content of matrix element sodium is directly measured by inductively coupled plasma atomic emission spectrometry (ICP-OES). The optimum dilution ratio is disposable obtained by optimizing the weight of the sample and the volume of the solution, so the sodium element detection signal intensity are regulated and controlled to a moderate level, in order to ensure that the method has good dynamic linear range. The paper have investigated the matrix effects, spectral interferences and background effects which caused by the coexistence of high concentrations of vanadium matrix, and then by taking preferred nebulizer pressure, plasma excitation power, observation height and other ICP spectrometer operating parameters, as well as optimizing and selecting the sodium element analysis spectral lines and its background correction and detection integration region, and combined with matrix matching and synchronization background correction measures, thus have effectively eliminated the transmission of the test solution injection, aerosol formation, ICP balance and excitation, background noise, element determination as well as many other interferences that caused by the alkali metal ions, high vanadium matrix and an argon molecule spectral band and other factors. The results show that: the calibration curve showed a good linear relationship when the sodium concentration below 20%, the correlation coefficient is equal to 0.997 5; RSD is less than 1.0%; recovery rate is 95.5% to 103.5% The determination results of the actual sample by ICP-OES method are consistent with flame atomic absorption spectrometry.