This paper (the first of a series of two) seeks to describe the experimental results of removing arsenic from dust collected in electrostatic precipitators of copper into the pyro-metallurgy gas cleaning systems. The first work corresponds to the treatment of dust contained in gas off generated in the copper Flash Smelting Furnace process (FS dust), while the second focuses on the treatment of dust generated from a Fluidized Bed Roasting Furnace (RP dust). The dust is complex sulphur-oxide-metals with concentrations of copper above 10 wt % and relatively high concentrations of silver. Due to the dust has an arsenic’s concentration above 5 wt %, makes it difficult to recover valuable metals through hydro-metallurgical processes or by direct recirculation of the dust into a smelting furnace. Thus, the development of pyrometallurgical processes aimed to reduce the concentration of arsenic in dust is the main purpose of this study, particularly the production of a material suitable for recirculation in smelting operations. The works conducted provide a detailed characterization of the dust, including Quantitative Evaluation of Minerals by Scanning Electron Microscopy (QEMSCAN), Scanning electron microscope-Energy Dispersive X-ray analysis (SEM/EDS), X-ray diffraction (XR-D), elemental chemical analysis using Atomic Adsorption (A. A.) and X-Ray Fluorescence (X-RF). By considering that arsenic volatilization requires a process of reduction-sulphidation-volatilization, the works explore the roasting of mixtures of copper concentrate/dust, sulphur/dust and pyrrhotite/dust. The degree of volatilization was determined by elemental chemical analysis of arsenic in the mixture after and before the roasting process. The results indicated the effect of parameters such as temperature, gas flow, gas composition and the ratio of mixtures (concentrate, sulphur or pyrrhotite)/dust on the volatilization of arsenic. The findings indicate that the concentration of arsenic in the FS dust can be reduced to a relatively low level (<0.5 wt %), allowing to the material to be recirculated into smelting processes.