The purpose of this placebo-controlled right-left intra-individual pre/post comparison study was to evaluate the efficacy of a new bi-layer composite membrane, composed of a layer of knitted cotton and a layer of semi-permeable polyurethane, developed in order to improve skin hydration. Eighteen healthy subjects entered the study. A T-shirt, dedicated to this study, was prepared and it was worn for 8 h, mimicking overnight wearing. Before and at the removal of the T-shirt an objective quantification of skin parameters was performed by measuring hydration, transepidermal water loss (TEWL) and skin surface pH, bilaterally, on the inner side of the forearm. Measurements were performed both at the interface between the skin and the bi-layer composite membrane or cotton and on the outer side of the membrane (to assess permeation of water and occlusive properties of the product) with and without a single application of a moisturizer. A statistically significant improvement of skin hydration, recorded on the stratum corneum underneath the bi-layer membrane versus cotton alone, was measured both with (p < 0.0001) and without application of the moisturizer (p < 0.002). TEWL was shown to decrease significantly on the side of the bi-layer membrane, if compared with cotton (p < 0.008), after application of the moisturizer. TEWL through the membrane showed no significant differences as compared to placebo, confirming the permeability of the fabric. Our data suggest that this bi-layer composite membrane can promote the hydration process of the stratum corneum, increasing the hydrating properties of the moisturizer agent.