Abstract: A method for the determination of 15 elements of TFe, SiO₂, CaO, MgO, Al₂O₃, TiO₂, P, S, Mn, V₂O₅, As, K₂O, Na₂O, Cu and Ni in high sulfur, arsenic iron ore by X-ray Fluorescence Spectrometry (XRF) was developed. Co in the form of cobalt glass powder was selected as the internal standard element for Fe determination. NH₄NO₃ served as the oxidant and Li₂CO₃ as the protective agent and were used for preventing the sulfur from volatilizing. Multi-kinds of standard references and artificial preparation iron ores were used for calibration. The almost overlapping spectral lines of Ti Κβ and V Κα were corrected by using the interfering curve method and the matrix effects were corrected by the theoretical alpha coefficient. The established method was possible to determine the TFe, the mass fraction of 5.29% S, 5.00% of V₂O₅ and 0.1% of As. The results were in accordance with certified values of standard reference materials. The RSDs met the requirements of lab qualify control, except the low content Na with RSD of <3.5%. The established method is a fast way to accurately obtain major and minor components in high S, As and V contents iron ores which is satisfied by the requirements of routine analysis.