Since the last decade, electrospinning is garnering more attention in the scientific research community, industries, applications like sensing (glucose, H 2 O 2 , dopamine, ascorbic acid, uric acid, neurotransmitter, etc.), biomedical applications (wound dressing, wound healing, skin, nerve, bone tissue engineering, and drug delivery systems), water treatment, energy harvesting, and storage applications. This review paper provides a brief overview of the electrospinning method, history of the electrospinning, factors affecting the electrospun nanofibers, and their morphology with different materials and composites (metals, metal oxides, 2D material, polymers and copolymers, carbon-based materials, etc.) used in the electrospinning technique with optical spinning parameters. Moreover, this paper deliberates the application of electrospun nanofibers and fibrous mats for sensing (electrochemical, optical, fluorescence, colorimetric, mechanical, photoelectric, mass sensitive change, resistive, ultrasensitive, etc.) in most illustrative representations. In the end, the challenges, opportunities of the electrospun nanofibers, and new direction for future progress are also discussed.