Development of high performance membranes for ethanol (EtOH) dehydration constitutes one of the main applications of pervaporation technology. In the present study, the properties of membranes derived from PAN were examined for this purpose. Heat treatment and variation of operational parameters were explored as viable strategies for enhancing the process performance. The characteristics of the membranes including morphology, thickness and sorption behavior were investigated in detail to identify their roles. Application of heat treatment with regards to polymer Tg resulted in membranes with distinct morphological and sorption characteristics. Increase in operational temperature was found effective for optimizing the opposing trends of permeate flux and separation factor. The maximum PSI value for the pristine PAN membrane was 5,564.0 g·m-2h-1, which occurred for operation at 50 ℃. Also, application of heat treatment led to drop in flux and increase in separation factor by which PSI reached 41.3 kg·m-2h-1, which was 7.5 times than that of pristine PAN membrane. This study demonstrates successful implementation of facile strategies for tuning the characteristics and performance of membranes derived from PAN for efficient dehydration of EtOH via pervaporation process.