The conventional electrospinning setup with a flat-plate collector and a spinneret connected to the high-voltage source provides nonwoven nanofiber mesh due to the chaotic motion of the electrospinning jet. The nonwoven mesh is suitable for a limited number of applications such as filter membrane. To broaden the field of applications of nanofibers, it is necessary to have an ordered and controlled nanofiber architecture. Alignment of the nanofibers can be obtained by mechanical movement of the collector and manipulation of the electric field lines via appropriate collector design or using auxiliary electrodes or a combination of both and by precision electrospinning. This chapter elaborates on the different alignment techniques and the combination of such techniques with a primary focus on the manipulation of the electric field. Section 7.3 sheds light on the applications of the ordered nanofiber architecture in the fields of healthcare, energy, defense, and sensors, among others. © 2020 World Scientific Publishing Co. Pte. Ltd.