The electrospinning method is adopted to prepare utralong PEO/stannic hydroxide composite nanofibers. Tin-oxide nanobelts can be obtained by calcination of the composite nanofibers in an open atmosphere. The nanobelts were characterized by a field emission scanning electron microscope, X-ray diffraction, a transmission electron microscope, a Raman spectromicroscope, and Fourier transform infrared spectroscopy. Microstructural analysis has shown that the nanobelts prepared consist of a continuous network of interconnected SnO2 grains. As a result, the SnO2 nanobelts possess a high surface area and continuous porosity, which may be applied for the fabrication of sensitive gas sensors.