The synthesis of continuous and low-siliceous ZSM-5 membranes was achieved without organic templates under mild conditions (a low temperature of 100 °C and ambient pressure). The resultant high-quality membranes with good water perm-selectivity were further applied in water-alcohol separation, exhibiting an extraordinarily high separation factor of above 10,000 and an improved water flux (3.43-6.88 kg m(-2) h(-1)) for ethanol and isopropanol aqueous azeotropes.