We report solution properties of the blend solutions of poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG)-POSS telechelic and its corresponding hybrid nanofibers prepared by electrospinning. The morphologies, microstructures, and wettability of the resulting PVA/PEG3.4k-POSS hybrid nanofibers are studied. The morphologies of the resultant PVA/PEG3.4k-POSS nanofibers are regular with the fiber diameter ranging from 610 +/- 110 to 810 +/- 280 nm. When the content of PEG3.4k-POSS telechelic increases above 20 wt.%, the beaded fiber morphologies are observed due to severe aggregations of the PEG3.4k-POSS telechelics as well as increased viscosity at higher concentration. In addition, the solution properties of pure PEG3.4k-POSS telechelic solution (ca. 3-5 wt.%) and PVA/PEG3.4k-POSS solutions blended with PVA are explored, and found to show the reversible turbid-to-transparent transition behavior with respect to the solution temperature. Water contact angle measurement of the PVA/PEG3.4k-POSS nanofiber membranes demonstrates an enhanced hydrophobic nature due to the incorporated POSS moieties.