The limited availability of antimony has increased the need for exploiting alternative sources to its direct extraction from stibnite deposits. Furthermore, introducing recovery techniques in industries where antimony is released in wastewaters leads to more responsible production routes. In this work, electrodeposition is employed to recover the antimony present in a secondary waste effluent of the copper electrorefining that is highly concentrated in hydrochloric acid. The electrochemical characterization of the system was conducted by voltammetry to identify a range of suitable operating conditions for the potentiostatic and galvanostatic electro-recovery of antimony. In potentiostatic mode, the progress of the secondary electrode reactions of hydrogen and chlorine evolution at potentials more cathodic than −0.38 V vs. Ag/AgCl causes the detachment and redissolution of the deposited antimony. Operating under galvanostatic control, similar effects were observed when the limiting current density is exceeded. Current efficiency and specific energy consumption values above 50 % and below 65 kW·h·kg−1, were achieved below the limiting current density (1.265 mA·cm−2). The operational range where electrodeposition of antimony is accelerated at increasing current densities can be broadened at intensified hydrodynamic conditions and higher concentrations of antimony. The detrimental effect of the hydrogen evolution reaction on the recovery of antimony decreases at high HCl concentrations.