The polarity of polyelectrolyte (PE) multilayer films is investigated with pyrene as a polarity-sensitive probe. Multilayer films of poly(styrene sulfonate) (PSS) and various polycations were prepared by the layer-by-layer self-assembly technique. Pyrene (PY) molecules were inserted into the films by exposing the multilayers to pyrene solutions. By this method a homogeneous distribution of pyrene molecules at low concentration within the film was obtained. The ratio of the fluorescence intensities of the first (I) to the third (III) vibronic band (Py-value) of the pyrene emission spectrum is employed here to determine the polarity of the PE films. PSS and poly(allylamine hydrochloride) (PAH) multilayer films yielded a pyrene value close to the solvent polarity of acetone, while multilayers of PSS and poly(diallyldimethylammonium chloride) (PDADMAC) displayed a value higher than the one corresponding to water. The pyrene values of the polyelectrolyte films were independent from the solvent employed for probe dissolving. Although no direct relationship between solvent polarity and dielectric constant (epsilon) is available, an estimate of the static dielectric constant of the films can be provided by comparing the Py-values of the films with those of various solvents. Changes in the humidity conditions of the film environment in a closed cell did not affect the film polarity. However, a drastic and irreversible reduction of polarity could be induced by actively drying the samples by a nitrogen flow.