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In this work, polyethylene glycol (PEG) with varying molecular weights was incorporated into the water-based polyurethane matrix (Permax232) to prepare Permax/PEG blend membranes for air dehumidification. The physical properties of the prepared membranes were characterized by FTIR, SEM, XRD and DSC. Furthermore, the influence of PEG molecular weight on the water vapor adsorption and permeability properties of the Permax/PEG blend membranes was investigated. The experimental results showed that blending PEG600 into the Permax232 matrix obtained optimal performance for air dehumidification. The water vapor sorption enthalpy and the permeation activation energy in the membranes were determined. Furthermore, Permax/20PEG600/PAN thin film composite membrane was developed via dip-coating method. The composite membrane showed superior water vapor permeance of 6578 GPU and water vapor/N 2 selectivity of 4909 and a satisfactory long-term stability, which had potential industrial application for energy efficient dehumidification. [Display omitted] • The PEG can be well dispersed in Permax232 matrix via hydrogen bonding. • The Permax/PEG membrane containing PEG600 was found to have optimal water vapor permeability. • With the relative humidity increased, the water sorption enthalpy and permeation activation energy increased. • The water vapor permeance of the composite membrane was 6578 GPU and the water vapor/N 2 selectivity was 4909. [ABSTRACT FROM AUTHOR]