© 2016 The Royal Society of Chemistry. In this contribution the photoreduction of silver ions coordinated onto a Langmuir-Blodgett monolayer is presented as an effective method for the deposition of the top contact electrode in metal/monolayer/metal devices. Silver cations were incorporated from an aqueous AgNO3 sub-phase of Langmuir films of 4,4′-(1,4-phenylenebis(ethyne-2,1-diyl))dibenzoic acid upon the transference of these films onto a metallic substrate. Subsequent irradiation of the silver-ion functionalized Langmuir-Blodgett films with 254 nm light results in the photoreduction of silver cations to produce metallic silver nanoparticles, which are distributed over the organic monolayer and exhibit a surface coverage as large as 76% of the monolayer surface. Electrical properties of these metal/monolayer/metal devices were determined by recording I-V curves, which show a sigmoidal behaviour indicative of well-behaved junctions free of metallic filaments and short-circuits. The integrity of the organic monolayer upon the irradiation process and formation of the silver top-contact electrode has also been demonstrated through cyclic voltammetry experiments.