Adsorption isotherms of pure vapors and vapor mixtures of water, methanol, and cyclohexane were studied using a synthesized 13X zeolite (FAU topology), by means of a DVS gravimetric vapor analyzer. These results were validated by GCMC calculations. The surface chemistry of the adsorbent was characterized by the thermodesorption of ammonia, and its textural properties were studied using nitrogen physisorption. The 13X zeolite was found to be strongly acidic (BrØnsted acid sites, Si/Al = 1.3) and its specific surface area around 1100 m2·g−1. Water was found to be able to diffuse within both the supercages and the sodalite cavities of the FAU structure, whereas methanol and cyclohexane were confined in the supercages only. The water/methanol sorption selectivity of the 13X zeolite was demonstrated by co-adsorption measurements. The composition of the water/methanol adsorbed phase could be calculated by assuming IAST hypotheses. This model failed in the case of the water/cyclohexane co-adsorption system, which is in line with the non-miscibility of the components in the adsorbed state. The sorption isotherms could be successfully simulated, confirming the robustness of the forcefields used. The 13X zeolite confirmed its a priori expected hydrophilic nature, which is useful for the selective adsorption of water in a methanol–water vapor mixture.