In electrospinning, outlook of fibrous assembly changes not only with the variation of collecting setups, but with the electrospinning process. For example, formation of multiple jets on a single droplet at special electrospinning conditions can produce several regions of fibrous webs simultaneously, which is bound to bring a great increase of production of nanofibers. The initiation method of multiple jets during electrospinning was derived through an experimental investigation by means of a high-speed camera, which was used to obtain the information of the shape change of a droplet along with process conditions, such as solution concentration, voltage and flow rate. Results showed that multiple jets could be initiated in a controlled manner when droplets experienced several cycles of dripping at relatively high voltages and flow rates in a certain concentration range. An interesting phenomenon of the auto-initiation of double jets was further observed in our experiment.