In this study, two hygroscopic materials, inorganic lithium chloride (LiCl) and organic triethylene glycol (TEG) were separately added to poly(vinyl alcohol) (PVA) to form blend membranes for air dehumidification. Water vapor permeation, dehumidification performance and long-term durability of the membranes were studied systematically. Membrane hydrophilicity and water vapor sorbability increased significantly with higher the hygroscopic material contents. Water vapor permeance of the membranes increased with both added hygroscopic material and absorbed water. Water permeation energy varied from positive to negative with higher hygroscopic content. This observation is attributed to a lower diffusion energy and a relatively constant sorption energy when hygroscopic content increases. Comparatively, PVA/TEG has less corrosive problems and is more environmentally friendly than PVA/LiCl. A membrane with PVA/TEG is observed to be highly durable and is suitable for dehumidification applications.