A novel thin film composite membrane with superior propylene dehumidification performance was prepared by coating a high hydrophilic organophosphorus acid ethylenediamine tetra(methylene phosphonic acid) (EDTMPA) doped poly(vinyl alcohol) (PVA) on polysulfione (PS) hollow fiber membranes. Experimental studies and molecular dynamics simulations were combined to probe the existing states and the transport mechanism of water in the membranes. Water vapor sorption experiments revealed that the enhanced dehumidification performance was governed by the diffusion process. Water states and water distribution were investigated by molecular dynamics simulation. At low EDTMPA content (<10wt%), states of the water were not obviously changed and the increase of water diffusion coefficient was mainly attributed to enlarged free volume of the membrane. At high EDTMPA content (10-30wt.%), the increase in the water diffusion coefficient mainly arose from the variations in the water states. Strong interaction between PVA and EDTMPA reduced the amount of water that bounded to the PVA and increased the proportion of free water. The diffusion coefficients of water increased with increasing proportion of free water, since the mobility of free water was higher than that of bound water. The permeance of water reached 997.7 GPU for the PVA-EDTMPA/PS membrane with a 20wt.% EDTMPA content when the proportion of free water was the highest, and the separation factor increased to infinity. (C) 2008 Elsevier B.V. All rights reserved.