Today, the most effective and suitable method to obtain molecular H2 is the extraction from mixtures where it is present, using gas‐sieving membranes. To this aim, the preparation and characterization of layered nano‐composites are described, made of alternated layers of positively charged Poly(Diallyl Dimethyl Ammonium chloride) (PDDA) and negatively charged graphene oxide (GO) nanosheets with high and tunable selectivity for H2 purification. The composites are assembled exploiting electrostatic interactions and the layer‐by‐layer technique; this study correlates permeance tests with changes in chemical composition and structure of the material using X‐rays Photoelectron Spectroscopy, X‐rays diffraction water contact angle, and surface zeta‐potential measurements. Thanks to its layered nature, the GO‐PDDA composite shows an excellent selectivity, allowing faster permeation of H2 as compared to CO …