In this paper, electrospinning method was adopted to prepare tin oxide nanofibers membrane with three kinds of novel precursor solution PVP/C12H24O4Sn, PVP/ C4H10OSn and PVP/SnCl4. The morphology, surface element, thermal analysis and crystal structure of the fibers membrane were investigated by SEM, EDS, TG-DTA and XRD. The results showed that the organic/inorganic hybrid nanofibers with an average diameter of 300～700 nm can be obtained by electrospinning. But after calcined at 600°C, the loose and porous tin oxide nanofibers membrane with an average diameter of 100～250 nm can be obtained only by using PVP/SnCl4 as preceusor solution, moreover, it showed good fiber forming property. From XRD spectra, it was found that the rutile structure tin oxide finally obtained without other crystalline forms.