Electrospinning is a versatile and accessible method for the production of submicron and nanoscopic fibers from organic polymers and inorganic compounds with a valuable extension to the industrial production of many high-end materials and products. There are suitable routes for preparing various inorganic oxides, carbides, sulfides, or even metallic nanofibers based on multi-step processes involving electrospinning. For electrospinning of the inorganic nanofibers, appropriate solutions must be prepared first. Usually, the inorganic precursors containing desired elements are dissolved with an organic, supporting polymer in a suitable solvent. The prepared solution is electrospuned into the so-called green composite nanofiber web. The following step is a high-temperature calcination in air, which removes the organic part and obtains pure inorganic oxide fibers. Nanofibers containing the W18O49 phase were prepared in the past by a combination of electrospinning of suitable substrate and solvothermal synthesis of desired W18O49 nanowhiskers from WCl6. So far, materials based on carbon, TiO2, and polyacrylonitrile nanofibers have been exploited as substrates for decoration by W18O49 nanowhiskers.