In this paper, we describe a new method for trace level Cd determination in complex environmental liquid samples. Thin layers activated with the extractant Aliquat 336 were prepared either by direct impregnation of commercial polymeric supports or by physical inclusion in a cellulose triacetate matrix, and both were effectively used to collect Cd present at low concentration in different aqueous matrixes. Quantitation of Cd contained in the thin layers was performed by high-energy polarized-beam energy-dispersive X-ray fluorescence. The effects of various experimental parameters such as layer composition, equilibration time, and instrumental conditions have been investigated. The analysis of different impregnated layers contacted with solutions ranging from 5 to 8000 microg L-1 Cd showed a linear response between the Cd concentration in the aqueous solutions and the metal present in the thin layer, with a detection limit of 0.7 microg L-1. The accuracy of the proposed method was confirmed by analyzing spiked seawater samples and a synthetic water sample containing, besides Cd, high amounts of other metal pollutants such as Ni, Cu, and Pb. The attained results were comparable to those obtained by anodic stripping voltammetry or inductively coupled plasma spectrometry.