Phase change PVA / PEG composite nanofibers were prepared by electrospinning, micro-morphology of PVA / PEG fibers with different weight content were analyzed, the phase change characteristics were also analyzed. The result showed that well distributed composite nanofibers which composed by PVA/PEG blend solution can be obtained by electrospinning.PVA fibreforming were influenced because of the existence of PEG, including bond, irregular block, small rough, uneven diameter distribution in fibers. PVA/PEG blend solution of 4:6 weight content was well fibreforming compared with other different weight content.The continuity of spinneret flow in electrospinning would directly affected by polymer solution consentrition and viscosity. Further research about which and the influence in fibers diameter and morphology will be explored. Composite nanofibers possessed reversible phase transition characteristics,Tm Essentially unchanged ,Tc were related to the weight percentage of PEG/PVA, at the same time, the enthalpy will increase along with the gradually increase in weight percentage of PEG.