In electrostatic charged spray, the electrostatic and polarization forces produced by high electrostatic field coupled with fluid forces act on the droplets which has a marked effect on the motion characteristics of the droplets. To analyse the charged twin-fluid spray structure, the effects of electrification on spray structure and aggrandizement of heat and mass transfer were discussed. Furthermore, PIV technology was employed to measure the gas-liquid twin-fluid electrostatic spray, and the collected flow image was send to the computer via data line by the image grabber card. The spray images data were analyzed by using Insight 3.3 software and then flow velocity and streamlines were gained. The experiment results indicated that the twin-fluid electrostatic spray has the special spray flow structure. The distinctly different structures with main jet flow section, up convolution section, down convolution section and influence section in the spray flow field were formed. The complicated eddy current effect comes into being in the twin-fluid electrostatic spray from single convolution phenomena, which could make the droplets contact with gas medium easy, and enhance the droplets absorbency.