Abstract:X-ray fluorescence spectrometry with fusion sample preparation method was used to determine the quantity of Mn, Si, P and Fe in electrolytic manganese. A Pt-Au crucible was coated with a protective layer made by melting lithium tetraborate and used as the container for electrolytic manganese. The Pt-Au crucible with electrolytic manganese was placed in a muffle furnace. BaO2 was used as the oxidizing agent and the electrolytic manganese was gradually oxidized with increased temperatures. Afterwards, the glass plate was made by fusion method and then tested by X-ray fluorescence (XRF) spectrometer to determine the content of Mn, Si, P and Fe elements in electrolytic manganese. The precision of the method for Mn, Si, P,Fe is 0.23%, 2.82% , 0.31% and 0.53%, respectively. Comparing with other analytical methods, XRF method is more stable. Since this method solved the problem caused by corrosion of Pt-Au crucible during sample preparation by fusion method, analytical errors of the method could be controlled completely within the acceptable limits of the national standard. Thus, this method allows to quantitatively determine all elements in electrolytic manganese with fast speed and good reliability.