Silver has grown its attraction of the scientists in microelectronic field recently. Electrochemical deposition of silver onto copper substrates by immersion method has been one of the keen topics. In this study, ethanol was used as the plating solution in which some chemicals were added. The silver deposits were characterized by a field emission scanning electron microscopy (FESEM), an atom force microscope (AFM), a transmission electron microscope (TEM) and a selected area electron diffraction (SAED). It was found that silver immersion using ethanol-based bath has good coverage feature. The highlands of the copper substrate are coated by silver particles whose sizes are around 12 nm, but those sizes at low-lying lands are a little smaller.