ZnWO4 fibers are fabricated by an electrospinning process. The phase, size and morphology, as well as the photocatalytic properties are studied carefully. The XRD, FTIR and XPS results confirm the formation of ZnWO4 with a monoclinic phase. The SEM and TEM images indicate that ZnWO4 fibers are comprised of lots of nanoparticles with diameters about 20 nm. The ZnWO4 fibers display high photocatalytic activities in degradation of RhB and photocurrent response under simulated sunlight irradiation. The recycling tests suggest the photocatalytic stability of ZnWO4 fibers. All of the results obtained by the work tell us that ZnWO4 fibers are excellent catalysts for the photocatalytic decomposition of pollutants. (C) 2016 Elsevier Ltd. All rights reserved.