The aim of the present work was to determine the influence of the microstructural evolution of copper single crystals with the initial orientations of <001> and <111> after cold drawing on their corrosion resistance. Transmission electron microscopy, X-ray diffraction, and electron backscattering diffraction were used to characterize the microstructural changes. To evaluate the corrosion resistance after deformation, open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization analyses were conducted. The microstructural observations showed the presence of dislocation cell structures and shear bands in deformed sample with initial orientation <001> single crystal, as well as a strongly-developed substructure in sample <111>. The material with initial orientation of <001> was more resistive in analyzed medium than material with the initial orientation of <111>.