The first data on native silver from the Rogovik Au–Ag deposit in northeastern Russia are presented. The deposit is situated in central part of the Okhotsk–Chukchi Volcanic Belt (OCVB) in the territory of the Omsukchan Trough, unique in its silver resources. Native silver in the studied ore makes up finely dispersed inclusions no larger than 50 μm in size, which are hosted in quartz; fills microfractures and interstices in association with küstelite, electrum, acanthite, silver sulfosalts and selenides, argyrodite, and pyrite. It has been shown that the chemical composition of native silver, along with its typomorphic features, is a stable indication of the various stages of deposit formation and types of mineralization: gold–silver (Au–Ag), silver–base metal (Ag–Pb), and gold–silver–base metal (Au–Ag–Pb). The specificity of native silver is expressed in the amount of trace elements and their concentrations. In Au–Ag ore, the following trace elements have been established in native silver (wt %): up to 2.72 S, up to 1.86 Au, up to 1.70 Hg, up to 1.75 Sb, and up to 1.01 Se. Native silver in Ag–Pb ore is characterized by the absence of Au, high Hg concentrations (up to 12.62 wt %), and an increase in Sb, Se, and S contents; the appearance of Te, Cu, Zn, and Fe is notable. All previously established trace elements—Hg, Au, Sb, Se, Te, Cu, Zn, Fe, and S—are contained in native silver of Au–Ag–Pb ore. In addition, Pb appears, and silver and gold amalgams are widespread, as well as up to 24.61 wt % Hg and 11.02 wt % Au. Comparison of trace element concentrations in native silver at the Rogovik deposit with the literature data, based on their solubility in solid silver, shows that the content of chalcogenides (S, Se, Te) exceeds saturated concentrations. Possible mechanisms by which elevated concentrations of these elements are achieved in native silver are discussed. It is suggested that the appearance of silver amalgams, which is unusual for Au–Ag mineralization not only in the Omsukchan Trough, but also in OCVB as a whole, is caused by superposition of the younger Dogda–Erikit Hg-bearing belt on the older Ag-bearing Omsukchan Trough. In practice, the results can be used to determine the general line of prospecting and geological exploration at objects of this type.