Electrospinning is a versatile and viable technique for ultra-thin fiber generation. Remarkable progress has been made with regard to the development of Electrospinning methods and the engineering of Electrospinning Nanofibre to suit or enable different applications. We aim to provide a comprehensive overview of Electrospinning, including principles, methods, materials and applications. We begin with a brief introduction to the early history of Electrospinning, followed by a discussion of its principle and its typical apparatus. Subsequently, we discuss the applications of electrospun Nanofibre, including their use as smart mattresses, filtration membranes, catalytic supports, energy harvesting / conversion / storage components, and photonic and electronic devices, as well as biomedical scaffolds. We highlight the most relevant and recent developments in the application of electrospun Nanofibre by focusing on the most representative examples.