As‐deposited Ag(10 nm)/glass films exhibited agglomerated nanocrystals with seemingly thick boundaries. Introduction of a TaNx layer below the Ag films resulted in dense and smooth structures, with a resistance at least three times lower than that of Ag/glass. For TaNx(10 nm)/Ag(10 nm)/TaNx(10 nm)/glass multilayer films, Auger electron spectroscopy results indicate that TaNx acts as an effective barrier restraining the diffusion of Ag. After annealing (up to 573 K), no outward diffusion of Ag through either TaNx layer was seen. However, partial oxidation of the outermost TaNx layer to form Ta2O5 was observed. The films showed promising optical properties with 73% transmittance in the visible region and ~15% average transmittance in the near‐infrared region. The optical data obtained here was in good agreement with simulated predictions. Copyright © 2013 John Wiley & Sons, Ltd.