A low cost, high selectivity asymmetric polyimide/polyethersulfone (PES) blend hollow fiber membrane, a method of making the membrane and its use for a variety of liquid, gas, and vapor separations such as deep desulfurization of gasoline and diesel fuels, ethanol/water separations, pervaporation dehydration of aqueous/organic mixtures, CO2/CH4, CO2/N2, H2/CH4, He/CH4, O2/N2, H2S/CH4, olefin/paraffin, iso/normal paraffins separations, and other light gas mixture separations. The polyimide/PES blend hollow fiber membrane is fabricated from a blend of a polyimide polymer and PES and showed surprisingly unique gas separation property with higher selectivities than either the polyimide hollow fiber membrane without PES polymer or the PES hollow fiber membrane without PES polymer for gas separations such as for H2/CH4, He/CH4, H2S/CH4, CO2/CH4 separations.