The effect of benzotriazole (BTAH) on the anodic dissolution of copper in 1 M HCl solution was investigated by using a rotating disc electrode (RDE) and a rotating hemispherical electrode (RHSE). It was shown that the presence of Cu(I) (CuCl or CuCl2−) on the copper surface is necessary to have the inhibitive effect of BTAH. Just below the current plateau, the effect of BTAH depends on the electrode geometry: for the RDE, the electrode surface remained partially active, the protection by BTAH occurred only on a ring at the edge of the electrode, whereas for the RHSE the surface is uniformly covered by a protective BTAH complex. For both electrodes without the presence of BTAH, a surface roughness develops during the copper electrodissolution that can be kinetically interpreted as a porous-like electrode with pores of finite size. In the presence of BTAH and for the RSHE, the size of the pores becomes semi-infinite.