The electroformation of Cu-Se phases, obtained by selenizing a thin film of copper deposited on the quartz/gold electrode system, was studied with an electrochemical quartz crystal microbalance (EQCM) and by cyclic voltammetry (CV) in an alkaline solution (0.05 M Na(2)B(4)O(7)) containing selenide ion. Potentiodynamic parameters showed that the formation of the initial Cu-Se phases (Cu(2-x)Se/Cu(3)Se(2)) is ruled by an irreversible diffusion controlled mechanism, where a first electron transfer is the rate-determining step. A CV study was also performed with a bulk copper electrode in 1 M NaOH solution containing selenide ion. The deconvolution of the anodic and cathodic I/E profiles corresponding to the electroformation and electroreduction of the Cu-Se film formed allowed us to establish that, depending on the anodic potential limit of the potentiodynamic scan, the Cu-Se phases formed were either a mixture of Cu(2)(-x)Se/Cu(3)Se(2) or Cu(2-x)Se/Cu(3)Se(2)/CuSe. An EQCM study showed that, during the initial stage of Cu-Se phase electroformation, water molecules were released from the electrode. In advanced stages of the process, when the electrode was completely covered by Cu-Se compounds, selenide anions were adsorbed on the formed phase. When the anodic potential limit was extended to -0.2 V, copper oxide compounds were formed. The analysis of the cathodic charge related to Cu-Se phase electroreduction and Energy Dispersive X-ray Spectroscopy (EDXS) analysis confirmed that when the anodic limit was -0.8 V, a mixture of different Cu-Se phases was formed. A I/t transient study performed with a bulk copper electrode in alkaline solution containing selenide established that the nucleation and growth mechanism (NGM) of the Cu-Se phases takes place through an initial bidimensional-instantaneous nucleation (IN2D), followed by four bidimensional-progressive nucleations (PN2D). These results and atomic force microscopy (AFM) experiences supported that the growth of the Cu-Se films occurs through a layer-by-layer mechanism.