Short-chain alcohols obtained by fermentation will play a key role in the industrial transformation toward green chemistry because of their use as fuel additives and fuels or for their conversion into olefins. The fermentation broth is often a highly diluted aqueous solution that requires separation, for instance, by liquid phase adsorption in nanoporous materials. However, entropy effects that prefer the adsorption of water might significantly reduce the separation efficiency─even in nanoporous materials with internal hydrophobicity. In this paper, we investigate this assumption by a case study on the separation of aqueous alcohol mixtures by liquid phase adsorption in CAU-10─an ultramicroporous metal-organic framework with internal hydrophobicity─using adsorption experiments and grand canonical Monte Carlo simulations to predict both the unary gas adsorption isotherms of ethanol, n-butanol, or water as well as the multicomponent liquid phase adsorption isotherms of their mixtures. It was observed that separation from the liquid phase is commonly driven by entropy effects and strong interactions between the guest molecules─both favoring the adsorption of water and thus complicating the separation of fermentation product by adsorption─while the internal hydrophobicity of CAU-10 is of comparatively little importance.