A near-infrared (NIR) -absorbing cyanine dye was used as a probe for in situ characterization of Nafion thin films. This NIR dye was very sensitive to changes in the hydrophobicity of the environment and proved to be very suitable for probing the Nafion coatings, which involve a two-phase structure of hydrophobic and hydrophilic zones. Sorption phenomena of water and aqueous alkali salt solutions by Nafion were investigated. For our study systems of thin-coating films prepared from 5% w t alcoholic solution of Nafion 117, the absorption spectrum was dominated by higher-order aggregates when in dry form. In pure water, the absorption maximum of the monomer dye appears at 773 nm and can be used as an indication of the swelling process of the film. The water uptake reaches saturation in only a few seconds. After the swelling process, an additional absorption band with a maximum a t 555 nm appears primarily at the expense of the NIR monomer dye absorption band. The peak transition process, which is a very slow process and is a strong function of the water content inside the matrix, can be used as an indication of the establishment of equilibrium between the two-phase structure due to the water uptake. Since the absorption maximum of the study system is around 800 nm, semiconductor lasers can be used. This technique shows high potential in other applications where polymers are used as support material, e.g., in situ thin-film thickness measurements. In the study, the feasibility of this approach was illustrated.