Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N-3(-), HPO2-, S-2(-), F-, Cl-,Br- and I- based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2- even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by I-, Cl- and S(2)(-)give a more surface roughness, while I- and N-3(-) offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications. (C) 2018 Elsevier B.V. All rights reserved.