Polymorphism control of PVDF has been realized through electrospinning. PVDF fibrous membranes with fiber diameter in the range of 100 nm to several micrometers were produced by telectrospinning and the crystal phase of electrospun PVDF fibres can be adjusted at the same time. Through the control of electrospin parameteers such as the solvent, electrospinning temperature, feeding rate, and tip-to-collecter distance, PVDF fibrous membranes containing mainly alpha- or beta- or gamma-phase could be fabricated successfually.