Ultra-thin silver films are susceptible to ambient environments and form grayish layers in the silver mirroring process. The poor wettability together with the high diffusivity of surface atoms in the presence of oxygen accounts for the thermal instability of ultra-thin silver films in the air and at elevated temperatures. This work demonstrates an atomic-scale aluminum cap layer on the silver to enhance the thermal and environmental stabilities of ultra-thin silver films deposited by sputtering with the assistance of a soft ion beam reported in our previous work. The resulted film consists of an ion-beam-treated seed silver layer of ∼1 nm nominal thickness, a subsequent silver layer of ∼6 nm thickness produced by sputtering alone, and an aluminum cap layer of ∼0.2 nm nominal thickness. Although the aluminum cap is only one to two atomic layers and likely non-continuous, it significantly improved the thermal and ambient environmental stability of the ultra-thin silver films (∼7 nm thick) without affecting the film's optical and electrical properties. The improved environmental stability is attributed to the cathodic protection mechanism and reduced diffusivity of surface atoms. The improved thermal stability is attributed to the reduced mobility of surface atoms in the presence of aluminum atoms. Thermal treatment of the duplex film also improves the film's electrical conductivity and optical transmittance by enhancing its crystallinity. The annealed aluminum/silver duplex structure has exhibited the lowest electric resistivity among the reported ultra-thin silver films and high optical transmittance similar to the simulated theoretical results.