The ultrafine composite fibers based on the composites of binary fatty acid eutectics and polyethylene terephthalate (PET) with varied fatty acid eutectics/PET mass ratios (50/100, 70/100, 100/100 and 120/100) were fabricated using the technique of electrospinning as form-stable phase change materials (PCMs). The five binary fatty acid eutectics including LA-MA, LA-PA, MA-PA, MA-SA and PA-SA were prepared according to Schrader equation, and then were selected as an innovative type of solid-liquid PCMs. The results characterized by differential scanning calorimeter (DSC) indicated that the prepared binary fatty acid eutectics with low phase transition temperatures and high heat enthalpies for climatic requirements were more suitable for applications in building energy storage. The structural morphologies, thermal energy storage and thermal stability properties of the ultrafine composite fibers were investigated by scanning electron microscope (SEM), DSC and thermogravimetric analysis (TGA), respectively. SEM images revealed that the electrospun binary fatty acid eutectics/PET ultrafine composite fibers possessed the wrinkled surfaces morphologies compared with the neat PET fibers with cylindrical shape and smooth surfaces; the grooves or ridges on the corrugated surface of the ultrafine composite fibers became more and more prominent with increasing fatty acid eutectics amount in the composite fibers. The fibers with the low mass ratio maintained good structural morphologies while the quality became worse when the mass ratio is too high (more than 100/100). DSC measurements suggested that the heat enthalpies of melting and crystallization of the ultrafine composite fibers increased gradually with increasing fatty acid eutectics amounts, but their phase transition temperatures had almost no obvious variation as relative to the corresponding fatty acid eutectics. Meanwhile, the characteristic temperatures and heat enthalpies of the ultrafine composite fibers varied with the different types of binary fatty acid eutectics. TGA results indicated that the degradation of electrospun binary fatty acid eutectics/PET ultrafine composite fibers with representative mass ratio of 100/100 had two steps and corresponded respectively to the degradations of binary fatty acid eutectics and PET polymer chains; and the charred residue at 700 degrees C of the composite fibers was lower than that of the neat PET fibers. It could be envisioned that the electrospun binary fatty acid eutectics/PET composite fibers would be extensively used for latent heat storage in the field of building energy conservation. (C) 2012 Elsevier Ltd. All rights reserved.