Europium was introduced into faujasite-type zeolites through ion exchange. The intensity ratio of the emission bands peaking at 590 and 614 nm changed depending on the amount of adsorbed water in zeolites. The results suggest that europium photoluminescence spectra could be a useful probe for providing information on a microenvironment in hydrated zeolites. The europium luminescence spectra of Fe–Al faujasite were measured as a function of the Fe content and compared with the water desorption temperatures to discuss the effect of Fe incorporation into the zeolite framework.