We describe the fabrication and characterization of tungsten oxide nanofibers using the electrospinningtechnique and sol-gel chemistry. Tungsten isopropoxide sol-gel precursor was incorporated into poly(vinylacetate)(PVAc)/DMF solutions and electrospun to form composite nanofibers. The as-spun composite nanofiberswere subsequently calcinated to obtain pure tungsten oxide nanofibers with controllable diameters of around100 nm. SEM and TEM were utilized to investigate the structure and morphology of tungsten oxide nanofibersbefore and after calcination. The relationship between solution concentration and ceramic nanofiber morphologyhas been studied. A synchrotron-based in situ XRD method was employed to study the dynamic structureevolution 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 gasdetection.