An analytical procedure for determination of Fe, Ti, V, Ni, Co and Cu, the most important constituents of the polymetallic ore has been developed. Twenty four powdered samples were prepared from the material taken in various places of the ore deposit. The samples were analyzed by wavelength dispersive (WD) and energy dispersive (ED) XRF method. The EDXRF method was applied using radioisotope source as well as a low power X-ray tube (Rh-anode) for excitation of the characteristic K-line radiation of the elements. A Si(Li) detector was used for the detection of radiation. The detection limits and precision of the analytical procedures, using reference materials, were estimated. The accuracy of the different XRF techniques is discussed. The developed analytical procedures based on the XRF method are rapid and quite simple. They can be useful for exploration data accumulation.