The method of ICP-OES for the direct determination of high content of rubidium in rubidium chloride solutions was studied through mass dilution method and optimizing parameters of the instrument in the present paper. It can reduce the times of dilution and the error introduced by the dilution, and improve the accuracy of determination results of rubidium. Through analyzing the sensitivity of the three detection spectral lines for rubidium ion, linearly dependent coefficient and the relative errors of the determination results, the spectral line of Rb 780.023 nm was chosen as the most suitable wavelength to measure the high content of rubidium in the rubidium chloride solutions. It was found that the instrument parameters of ICP-OES such as the atomizer flow, the pump speed and the high-frequency power are the major factors for the determination of rubidium ion in the rubidium chloride solutions. As we know instrument parameters of ICP-OES have an important influence on the atomization efficiency as well as the emissive power of the spectral lines of rubidium, they are considered as the significant factors for the determination of rubidium. The optimization parameters of the instrument were obtained by orthogonal experiments and further single factor experiment, which are 0.60 L·min-1 of atomizer flow, 60 r·min-1 of pump speed, and 1 150 W of high-frequency power. The same experiments were repeated a week later with the optimization parameters of the instrument, and the relative errors of the determination results are less than 0.5% when the concentration of rubidium chloride ranged from 0.09% to 0.18%. As the concentration of rubidium chloride is 0.06%, the relative errors of the determination results are -1.7%. The determination of lithium chloride and potassium chloride in the high concentration of the aqueous solutions was studied under the condition of similar instrument parameters. It was found by comparison that the determination results of lithium chloride are better than that of potassium chloride and rubidium chloride. The method of ICP-OES used for determination of high content of rubidium is fast and simple for operation, and the results are accurate. It is suitable for studying the equilibrium in the salt-water system containing rubidium and for analysis of products of rubidium with high content.