Thermoregulation of gas transport using electrospun fiber membranes is demonstrated experimentally for the first time. The fiber membranes comprise three layers: a middle layer of electrospun polystyrene sandwiched between two outer layers of electrospun cellulose acetate mat as supports, bonded together by hot pressing. The electrospun polystyrene layer serves as a phase change material that blocks transport of gases though the membrane when the fibers de-vitrify. The membrane exhibited a reduction in oxygen flux at temperatures in excess of 140 degrees C. Using a blend of polysulfone and polystyrene resulted in an upward shift of the transition temperature to 250 degrees C. Modeling of transport was performed to estimate the impact of the morphological properties of the membranes such as tortuosity, fiber diameter, and porosity. (C) 2014 Elsevier Ltd. All rights reserved.