In this study, four fatty acids of lauric acid (LA), myristic acid (MA), palmitic acid (PA), and stearic acid (SA) were selected to prepare six binary fatty acid eutectics of LA-MA, LA-PA, LA-SA, MA-PA, MA-SA, and PA-SA; thereafter, electrospun ultrafine composite fibers with the binary fatty acid eutectics encapsulated in the supporting matrices of polyethylene terephthalate (PET) were prepared as innovative form-stable phase change materials for storage and retrieval of thermal energy. The morphological structures and thermal energy storage properties of the ultrafine composite fibers were characterized by scanning electron microscope (SEM) and differential scanning calorimeter (DSC), respectively. The SEM results indicated that the fibers had the cylindrical morphology with diameters of 1–2 µm; some had smooth surfaces, while others had wrinkled surfaces with grooves. The DSC results indicated that the phase transition temperatures of binary fatty acid eutectics were lower than those of individual fatty acids; the enthalpy values associated with melting and crystallization for the eutectics encapsulated in the composite fibers were considerably reduced, whereas there were no appreciable changes on the phase transition temperatures. Copyright © 2012 John Wiley & Sons, Ltd.