This paper refers to the application of XRF method for the simultaneous determination of arsenic and selected metals from waste samples resulted from the dismanlting of distilleries in the perimeter of Azomures S.A., Mures County, Romania. The dismantling operation was carried out by a specialized Romanian company, and from this operation resulted several refractory construction wastes, such as sands with a very high content of arsenic and its chemical compounds. In order to determine the arsenic and other metals concentration, the energy-dispersive X-ray fluorescence (ED-XRF) spectrometric technique was employed. Application of the ED-XRF method was performed in an accredited laboratory for the determination of toxic substances from various samples, using a Genius portable XRF (p-XRF) spectrometer manufactured by Skyray Instruments Inc.