Abstract: Introduced determination methods of SiO₂，Na₂O，K₂O，and S in sodium silicate by X-ray fluorescence spectrometry in the helium atmosphere.Studied sampling way and quantity，setting of instrumental parameters，ascertainment of element spectral background，and correction of spectral overlapping and absorption-enhancement.Each component was fitted in one working curve.The combination of the fundamental parameter method and empirical coefficient method was mainly used to correct the absorption enhancement and spectral overlapping effects of the coexisting elements.The optimum test conditions were confirmed through investigating the precision and accuracy of the determination methods.Comparing with chemical method，the accuracy of this method could meet the analysis error demand of the national standard method.

Key words: X-ray fluorescence spectrometry, sodium silicate, helium, absorption-enhancement