Electrospinning has been regarded as a convenient and efficient technique for preparing polymer fibers. The obtained electrospun fibers present a great application promising in various areas including filtration, distillation, and protect clothing due to its small fiber diameters, high specific surface area, easy-to-modify surface characteristics, and controllable fiber structure. At present, the fiber with single circular section was difficult to meet the needs of practical applications in many occasions. The development of electrospun fibers with diversified structures has become an important research direction. In this chapter, we summarized the methods and mechanisms in the regulation of electrospun fiber from four aspects: spinning solutions, spinning process parameters, spinning nozzle structure, and receiving device (collector).