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. 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%.