Ultrafine phase change fibers based on polyethylene glycol (PEG)/cellulose acetate (CA) blends in which PEG acts as a model phase change material (PCM) and CA acts as a supporting material, were successfully prepared via electrospinning. The effect of PEG content on the morphology, crystalline properties, phase change behaviors and tensile properties of the composite fibers was studied systematically by field-emission scanning electron microscopy (FE-SEM), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and a tensile tester, respectively. The SEM observation indicates that maximum PEG content in the fibers could reach up to 70 wt%, and the morphology and average diameter of the composite fibers vary with PEG content. Thermal analysis results show that the latent heats of the phase change fibers increase with the increasing of PEG content in the fibers, and the PEG/CA fibers with high enthalpies have a good capability to regulate their interior temperature as the ambient temperature alters. Therefore, the developed phase change fibers have enormous applicable potentials in thermal energy storage and temperature regulation. (C) 2011 Elsevier Ltd. All rights reserved.