The process of electrospinning is over a century old, yet novel material and method achievements, and later the addition of nanomaterials in polymeric solutions, have spurred a significant increase in research innovations with several unique applications. Significant improvements have been achieved in the development of electrospun nanofibrous matrices, which include tailoring compositions of polymers with active agents, surface functionalization with nanoparticles, and encapsulation of functional materials within the nanofibers. Recently, sequentially combining fabrication of nanofibers with 3D printing was reported by our group and the synergistic process offers fiber membrane functionalities having the mechanical strength offered by 3D printed scaffolds. Recent developments in electrospun nanofibers are enumerated here with special emphasis on biomedical technologies, chemical and biological sensing, and energy harvesting aspects in the context of e-textile and tactile sensing. Energy harvesting offers significant advantages in many applications, such as biomedical technologies and critical infrastructure protection by using the concept of finite state machines and edge computing. Many other uses of devices using electrospun nanofibers, either as standalone or conjoined with 3D printed materials, are envisaged. The focus of this review is to highlight selected novel applications in biomedical technologies, chem.-bio sensing, and broadly in energy harvesting for use in internet of things (IoT) devices. The article concludes with a brief projection of the future direction of electrospun nanofibers, limitations, and how synergetic combination of the two processes will open pathways for future discoveries.