in Wiley InterScience (www.interscience.wiley.com).As an aim toward developing novel class of form-stable polymer-matrix phase change materials for thermal energy storage, ultrafine composite fibers based on cellulose acetate and polyethylene glycol (PEG) with five different molecular weight (M n ) grades were prepared by electrospinning. The effects of M n of PEG on morphology, thermal properties and mechanical properties of the composite fibers were studied by field emission scanning electron microscopy, differential scanning calorimetry, and tensile testing, respectively. It was found that the composite fibers were smooth and cylindrical shape, with the average diameters ranging from about 1000 to 1750 nm which increased with M n of PEG. Thermal analysis results showed that the composite fibers imparted balanced thermal storage and release properties in different temperature ranges with the variation of M n of PEG. Thermal cycling test indicated that the prepared composites had excellent thermal stability and reliability even they were subjected to 100 heating-cooling thermal cycles.