The invention relates to an asymmetric electrostatic field coupling pervaporation device, which comprises a raw material chamber, a permeation chamber, a membrane and electrodes, wherein an asymmetric electrostatic field can be produced by the electrodes; the electrodes comprise a plate electrode and a needle-shaped electrode; and direct current voltage of 101-104V is applied to the electrodes. Polar molecules in raw material liquid permeate through the membrane at a higher speed than that in a case of only using chemical potential gradient as thrust power to be vaporized on the surface of the membrane to form permeate steam under the double actions of chemical potential gradient and electric potential gradient formed by the asymmetric electrostatic field produced by the electrodes. The invention also relates to an asymmetric electrostatic field coupling pervaporation method.