Despite their excellent electrical and optical properties, Ag nanowires (NWs) suffer from oxidation when exposed to air for several days. In this study, we synthesized a Cs carbonate-incorporated overcoating layer by spin-coating and ultraviolet curing to prevent the thermal oxidation of Ag NWs. Cs incorporation increased the decomposition temperature of the overcoating layer, thus enhancing its thermal resistance. The effects of the Cs carbonate-incorporated overcoating layer on the optoelectrical properties and stability of Ag NWs were investigated in detail. The Ag NW electrode reinforced with the Cs carbonate-incorporated overcoating layer exhibited excellent thermal oxidation stability after exposure to air for 55 days at 85 °C and a relative humidity of 85%. The novel overcoating layer synthesized in this study is a promising passivation layer for Ag NWs against thermal oxidation under ambient conditions. This overcoating layer can be applied in large-area optoelectronic devices based on Ag NW electrodes.