A noncovalently bound multilayered thin film in which individual layers are linked by metal ligand interactions undergoes a photochemically initiated permanent change in surface wettability. The film consists of three separate layers: a SAM on gold of 4-[(10-mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid, a layer of Cu(II) ions that are deposited onto the SAM and bind symmetrically in the site provided by the two carboxylate groups and the pyridyl nitrogen atom, and a layer of cis-2,2′-dipyridylethylene, which caps the Cu(II) layer by complexation through both pyridyl nitrogen atoms (Film I). Photoexcitation of the film in chloroform at 300 nm leads to substantial cis-trans isomerization as indicated by conductivity, impedance, grazing incidence IR, and contact angle measurements. The latter show a decrease in contact angle (increase in wettability) of 17°, which is attributed to exposure of both the underlying Cu(II) layer and one of the pyridyl ring nitrogen atoms following isomerization to the trans isomer. Copyright © 2004 American Chemical Society.