The uniform large micropores of hydrothermally stable Y zeolites are used widely to confine both polar and non-polar molecules. This paper compares the physisorption of water, methanol, cyclohexane, benzene and other adsorbates over various Y zeolites. These adsorbents are commercial products with reproducibly controllable physical and chemical characteristics. Results indicate that the type I isotherms typical for micropore adsorption can turn into type II or type III isotherms depending on either or both the hydrophobicity of the adsorbent and the polarity of the adsorbate. Methanol produced a rare type V isotherm not reported over zeolites before. Canonical and grand canonical Monte Carlo molecular simulations with Metropolis importance sampling reproduced the experimental isotherms and showed characteristic geometric patterns for molecules confined in Na-X, Na-Y, dealuminated Y, and ZSM5 structures. Adsorbate—adsorbate interactions seem to determine the micropore condensation of both polar and non-polar molecules. Exchanged ions and lattice defects play a secondary role in shaping the adsorption isotherms. The force field of hydrophobic Y appears to exert an as yet unexplored sieving effect on adsorbates having different dipole moments and partial charge distributions. This mechanism is apparently different from both the monolayer formation controlled adsorption on hydrophobic mesopores and macropores and the polarizability and small-pore opening controlled micropore confinement in hydrophobic ZSM5.