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A combination of electrochemistry and luminescence methods was exploited to obtain information on the electrochemical activity and homogeneity of Nafion Langmuir−Blodgett films. The redox behavior of the Ru(bpy)₃²⁺ probe incorporated in the Nafion film was monitored by epifluorescence microscopy. The photoluminescent images, recorded by a charge-coupled device (CCD) camera, reflect the distribution of the probe in the film, which resulted as very uniform, particularly in comparison with spin-coated films. Apparent diffusion coefficients (D_app) determined by cyclic voltammetry for films of less than 10 layers are in the range of 1 × 10⁻¹² to 8 × 10⁻¹² cm² s⁻¹, that is, 2 orders of magnitude lower than values reported in the literature for spin-coated Nafion films. The application to the electrode of a potential able to oxidize the luminescent Ru(bpy)₃²⁺ to the nonluminescent Ru(bpy)₃³⁺ switched off the photoluminescence with a response time that for the LB films was much shorter than that for the spin-coated ones. Experimental evidence and calculations indicate that lowering of the film thickness down to the nanometric level is very effective in shortening the switching time, notwithstanding the lowering of the D_app value in LB films.