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The dropping mechanism in the electrospinning process is elucidated. A moving jet becomes thinner at the initial stage due to the acceleration caused by the electrostatic force. When the jet diameter reaches a threshold, beyond which the jet breaks into drops and daughter jets, dropping occurs. The drops will finally form microspheres. Effects of applied voltage, flow rate, polymer’s concentration and receptor’s distance on the dropping process are theoretically analyzed and experimentally verified. This paper gives a general strategy for fabrication of smooth fiber, microspheres, and their mixture.