A three-layer thin film nanofibrous pervaporation composite (TFNPVC) membrane was prepared by sequential deposition using electrospraying/electrospinning. The poly(vinyl alcohol) (PVA) top barrier layer was first electrosprayed on aluminum foil and its thickness can be easily controlled by adjusting the collecting time. Next a polyacrylonitrile (PAN) nanofibrous scaffold was deposited by electrospinning as a mid-layer support. A nonwoven PET layer is used to complete the composite membrane. The pervaporation desalination performance of TFNPVC membranes was tested using NaCl solutions at 100. Pa and at room temperature. The TFNPVC membranes show excellent desalination performance (high water flux and salt rejection >. 99.5%) for different salt concentrations with virtually no change in performance after 50. h of operation. © 2014 Elsevier B.V.