The aim of this work was to produce a thin SnO2 film by a technique combining the sol-gel method and electrospinning from a solution based on polyvinylpyrrolidone and a tin chloride pentahydrate as a precursor. The spinning solution was subjected to an electrospinning process, and then the obtained nanofiber mats were calcined for 10 h at 500°C. Then, the scanning electron microscopy morphology analysis and chemical composition analysis by X-ray microanalysis of the manufactured thin film was performed. It was shown that an amorphous-crystalline layer formed by the SnO2 nanofiber network was obtained. Based on the UV-Vis spectrum, the width of the energy gap of the obtained layer was determined.