In this work, PVA /PEG phase change composite nanofibers were prepared by electrospinning at room temperature. The diameter and morphology of PVA / PEG nanofibers were studied by scanning electron microscopy (SEM) to research the relationship with different weight content, applied voltage, collect distance and added ionic salt on fiber diameter and fiber network morphology. The result showed that PVA/PEG blend solution of 4:6 weight content, a fixed electric field of 15kV/10cm was the best process parameters. Under this electrospinning conditions, we have got the well distributed composite nanofibers which composed by PVA/PEG blend solution. The phase change characteristics of PVA/PEG composite nanofibers were also analyzed by using DSC method. Composite nanofibers possessed reversible phase transition characteristics, different ratios of PEG component(Mw = 2000,4000) may little changed Tm and Tc, but the influence was not very obvious as we expected.