Antimony and arsenic concentrations and their oxidation states (Sb(III), Sb(V), As(III) and As(V)) in copper electrorefining electrolyte can affect copper cathode quality through the formation of floating slimes. A laboratory-scale pilot plant was operated to remove Sb from commercial electrolyte. The pilot plant consisted of a pre-treatment process with copper shavings followed by ion exchange. The results indicated that Sb(III) was removed from copper electrolyte completely, while Sb(V) was partially eliminated. The concentrations of As(III) and As(V) were not affected, and the poisoning of the ion exchange resin by Fe(III) was avoided by pre-reduction to Fe(II) by copper shavings. The operation configuration of the pilot plant was applied to the design of an industrial plant for Sb/Bi removal at the Atlantic Copper Refinery in Huelva, Spain. The evolution of Sb, Fe and As species in the commercial electrolyte was monitored prior to and after the installation of the Sb/Bi removal plant. The results show a ca. 45% decrease in total Sb content (from 0.29 g L−1 to 0.16 g L−1) in the electrolyte. This reduction is more noticeable for Sb(III), whose concentration decreased from 0.18 g L−1 to 0.09 g L−1, whereas Sb(V) concentration diminished from 0.11 g L−1 to 0.07 g L−1. The resin also retained ca. 75% of the Bi content (0.15-0.22 g L−1). The total As increased during the study period (from 7.7 to 9.0 g L−1) due to changes in plant inputs. Arsenic was predominantly As(V) (ca. 93-95%). The total Fe concentration experienced little variation (0.9-1.1 g L−1) with Fe(II) being the main species (ca. 94-96%).