Electrospray is a process that relies on the electrostatic force to break the liquid into fine charged droplets. Electrospray ha several features by contrast with other atomization techniques. Since the size distribution of the droplets in electrospray is monodispersity when the spray operates under the Taylor-cone mode, and it is well controllable, the electrospray is applied in many fields such as material process, mass spectrometry technique, drag delivery, and ink jet print etc. In this paper, Dantex Flowmap 1500 PIV system with double-pulse Nd:YAG laser was used to measure the whole instantaneous velocity field of the electrospray droplets. The measuring results show that many effects, such as the applied voltage, flow rate, and temperature, will influence on the velocity distribution of the drops. The velocity distribution of the electrospray dorps is axisymmetric. The highly applied voltage will lead the droplets to accelerate during falling.