A zirconium tungstate (ZrW2O8) precursor was synthesized by a novel sol-gel method with zirconium oxychloride and tungstic acid as the zirconium and tungsten sources, respectively. Heat treatment at 600oC for 10 hours was adequate to crystallize the precursor. Use of excess zirconium source and the concentration of hydrochloric acid were found to affect the phase purity and crystallization temperature of ZrW2O8. Sizes of particles obtained were in submicron range in the absence of a microemulsion system. On the other hand, using water/oleylamine/hexane reverse micelle microemulsion technique monodispersed particles with sizes between 10 to 100nm were obtained. Nanoparticles were then successfully dispersed in a solvent with a carrier polymer to produce ZrW2O8 nanofibers with electrospinning technique.