This study investigated the effect of 2-butoxyethanol (BE) as a nonsolvent additive, relative humidity and air contact time on the structure formation of microfiltration membranes, permeation and morphology properties in phase inversion process. The membranes were prepared by using polyethersulfone (PES)/Dimethyl formamide (DMF)/p-toluenesulfonic acid (TSA)/Polyvinylpyrrolidone (PVP)/BE casting solution and water coagulant. Casting solutions containing various concentration of BE were exposed to a water vapor, under 60 and 80% of relative humidity for 40 and 90 sec, which would be absorbed on. The correlations between the membrane permeation properties and surface/inner structures of membrane were investigated. The characterization of membranes was carried out by a capillary flow porometer, a FE-SEM and a water permeation test apparatus. The surface structure of PES membranes was affected by the exposure time as well as the relative humidity strongly. Furthermore, the addition of BE helped control surface and inner structure at certain humidity and exposure time.