Bicomponent polymer solutions were prepared from two immiscible polymers, poly(vinylalcohol) (PVA) and polyacrylonitrile (PAN), and then Used to prepare films and electrospun fibers. The miscibility and the surface morphology of the bicomponent polymer systems were determined. There was a strong relationship between the diameter of the electrospun fibers and the blend ratio used. By applying selective dissolution, using Solvents Such as hot water, acetic acid, or N,N-dimethylformamide, to the films and fibers, one polymer component was removed Selectively without affecting the other component. This resulted in a decrease in the diameter of the electrospun fibers and the formation of grooves, pores, and craters on the fiber Surface. The width of the grooves decreased as the bicomponent polymer content increased. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 274-282, 2009