We describe the fabrication and characterization of tungsten oxide nanofibers using the electrospinning technique and sol-gel chemistry. Tungsten isopropoxide sol-gel precursor was incorporated into poly(vinyl acetate)(PVAc)/DMF solutions and electrospun to form composite nanofibers. The as-spun composite nanofibers were subsequently calcinated to obtain pure tungsten oxide nanofibers with controllable diameters of around 100 nm. SEM and TEM were utilized to investigate the structure and morphology of tungsten oxide nanofibers before and after calcination. The relationship between solution concentration and ceramic nanofiber morphology has been studied. A synchrotron-based in situ XRD method was employed to study the dynamic structure evolution of the tungsten oxide nanofibers during the calcination process. It has been shown that the as-prepared tungsten oxide ceramic nanofibers have a quick response to ammonia with various concentrations, suggesting potential applications of the electrospun tungsten oxide nanofibers as a sensor material for gas detection.