Electrospinning is a potent "top-down" nanofabrication method and has been explored by many researchers in recent decades because it is an efficient, versatile, simple, and low-cost route to prepare nanofibers. Nanofiber membranes generated by electrospinning have been used in various fields including tissue engineering, wound dressing, biosensing, theranostics, and functional textiles. Here we summarize the development of multifluid electrospinning processes, including coaxial, Janus and triaxial electrospinning, and the applications of these techniques. Complex nanostructures prepared by multifluid electrospinning are considered. The key parameters that affect the electrospinning process are introduced, and a discussion of both equipment and solution parameters is presented.