With the action of catalyst and cosolvent, a series of hydroxyl-terminated polydimethylsiloxane (HPMS) based polyurethane (PU) micro-emulsion were gotten by surfactant-free copolymerization. They were successfully prepared by reacting isophorone isocyanate, poly(tetramethylene glycol), and HPMS with N-methyldiethanolamine (MDEA) as chain extender and trimethylolpropane (TMP) as crosslinker. After neutralizing with dimethyl sulfate and inversing the emulsion polymerization with deionized water, a series of microemulsions were obtained. The emulsions were then cast into membranes named as PU–HPMS. The mechanical properties and water absorption of the PU–HPMS were determined and simultaneously the effects of the content of hard segment, solvent, TMP, MDEA, HPMS, and the molecular weight of soft segment were studied. It is noticed that the tensile strength decreased and elongation at break increased in the HPMS/PU when compared with pure PU, which confirm that PU was end-capped with PDMS. It is also noticed that water absorption increased in the HPMS/PU when compared with pure PU. As HPMS content increased from 0.0 to 25.0 wt %, the surface free energies decreased from 0.3446 to 0.2317 mN/cm and water absorption decreased from 11.2% to 0.14%. The surface free energies of the membranes were decreased by more than 32.76%, which demonstrate that the membrane surfaces have excellent water and oil repellency. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 40–46, 2006