Potentiodynamic electrochemical tests and surface analysis technics, such as scanning electronic microscope (SEM), energy dispersive spectrum (EDS) and X-ray diffraction analysis (XRD), were applied to investigate the microstructure and corrosion behavior of Ag-Cu-Zn-Ni alloys in Na2S solution. The results reveal that the α-Ag phase is the main matrix of the studied silver alloys. The second phase of Ag-4Cu-0.3Ni and Ag-3Cu-Zn-0.3Ni/Ag-6Cu-Zn-0.3Ni are respectively CuNi and CuNi(Zn) phases. The second phases of Ag-6Cu-Zn-0.3Ni are well-distributed, which leads to an improvement in the corrosion resistance in Na2S solution.