Dispersed solutions of poly(vinylidene fluoride) (PVDF)/polycarbonate (PC) in the mixed solvent of N,N-dimethylformamide (DMF)/tetrahydrofuran (THF) were used to electrospin in order to discuss the relationship between the properties of the polymer dispersions and the morphology of the obtained ultrafine fibers. With the changes of the mass ratio of PVDF/PC, the relative molecular mass of PVDF, and the volume ratio of DMF/THF, the morphology and the microstructure of the prepared PVDF/PC ultrafine fibers altered in accord with the viscosity, surface tension, and conductivity of the PVDF/PC dispersions. When the PVDF/PC mass ratio varied from 9/1 to 5/5, the ability of the polymer chain entanglement in PVDF/PC dispersion decreased as to the lower relative molecular mass of PC and higher chain rigidity, which lead to the formation of the beaded fibers together with the distinct core/shell structure. Similar phenomenon was also found when the lower molecular mass of PVDF was used instead of a higher one. Though the change of DMF/THF volume ratio did not specifically contribute to the properties of PVDF/PC dispersions, the accelerated evaporation and solubility of the mixed solvent by the THF amount increasing was feasible to generate the uniform fibrous morphology and the distinct core/shell structure. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 372-380, 2010