Electrospinning, the key process in developing nanofiber membranes, must enable the production of high-performing, recyclable, and reusable materials to meet the demands of diverse applications. The complex relationship between the various factors that influence the morphology and the performance of electrospun nanofiber membranes is the focus of this book chapter. The performance of the electrospinning process and the properties of the resulting nanofiber membrane can be affected by factors such as polymer solution properties, process parameters, and environmental conditions. Understanding these factors allows researchers to achieve controlled structures and desired functionalities in nanofiber membranes. Elucidating these relationships will allow researchers to precisely tailor nanofibers through optimization approaches such as hybrid, mixed matrix, and multilayer nanofiber membrane designs and unlock their full potential for a wide range of applications. This will unlock their full potential for a variety of future applications. A better understanding of nanofiber formation methods, the development of hybrid nanofiber membranes, and the advancement of engineering electrospinning techniques to meet future needs will determine the next generation of nanofiber membranes.