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Copper is an active electrocatalyst for various energy conversion reactions, but its performance depends on the structure of the active surface sites. In this work, we propose a simple strategy to tailor both the roughness and the active site's geometry of copper. To modify the surface of copper, we oxidize and reduce a copper polycrystalline electrode in 0.1 M solutions containing both sodium fluoride and sodium chloride with different chloride/fluoride molar ratios: (0.1‐x) M NaF+x M NaCl. To address the anion effect on the changes in surface geometry, we recorded the voltammetric fingerprints of the modified electrodes using lead underpotential deposition (UPD). The voltammetric analysis suggested that while chloride induces (n10) sites, fluoride promotes an increase in the active surface area and the growth of low‐coordinated sites with (110) or (111) geometry. Solutions containing both fluoride and chloride anions induced (n10) motifs covered by nanometric clusters, as observed by scanning electron microscopy, forming a highly defect‐rich surface. Our work provides a direct link between electrochemical response and ex‐situ structural characterization, and compares, in detail, the effect of chloride and fluoride on the surface nanostructuring of copper. [ABSTRACT FROM AUTHOR]