A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels. The model separation test on columns shows that an ultra-pure ethanol (99.9%) can be obtained from the mixture of ethanol/water (95:5). Additionally, after refluxing the desolvated sample in 95% ethanol at 60 °C for 5 h, the purity of ethanol rises up to 97.43%, which is obviously higher than 96.56% for 4 Å molecular sieves.