The effect of Mg in Ag(Mg)/SiO2/Si multilayers on adhesion, agglomeration, and resistivity after annealing in vacuum at 200 to 500 have been investigated. The annealing of Ag(Mg)/SiO2/Si multilayers produced surface and interfacial MgO layers, resulting in MgO/Ag(Mg)/MgO/SiO2/Si structure. The presence of surface MgO provided the passivation against air, thus leading to the significantly enhanced resistance to agglomeration. In addition, the resistivity of Ag(Mg) film decreased by lowering Mg content and increasing the annealing temperature as well. Furthermore, Ag adhesion to SiO2 was improved due to the formation of the interfacial MgO layer resulting from the reaction of segregated Mg with SiO2. Also, the negligible solubility of Si in Ag prevented the dissolution of free silicon produced from the reaction, Mg + SiO2 = MgO + Si, which was in contrast with the dissolution of a significant amount of silicon released from the SiO2 substrate in Cu(Mg)/SiO2/Si multilayers after annealing at high temperature, e.g., 400. The dissolved Si in Cu caused the rapid increase in resistivity in Cu(Mg)/SiO2/Si.