Electrospinning is a promising technology for creating nano/microfiber-based membranes with high surface area, porosity, and favorable mechanical properties, which can be used in energy-autonomous wearable sensing systems. This review discusses how electrospinning can be used in energy-autonomous wearable wireless sensing systems, covering electrospinning technology, fundamental mechanisms, and applications in energy scavenging, human physiological signal sensing, energy storage, and antenna for data transmission. The review also discusses combining wearable electronic technology with textile engineering to create superior wearable devices and increase future collaboration opportunities. It addresses challenges related to testing for market-ready products. Electrospinning enables the fabrication of ultrafine/intricate three-dimensional fiber networks with diameters ranging from nanometers to micrometers. These fibers can be easily collected as nonwoven mats or aligned into patterns with desirable wearable properties, such as breathability, washability, biocompatibility, stretchability, and flexibility. These fibers can serve as construction blocks for a variety of components, including sensors, electrodes, and energy storage elements. Electrospinning allows for the incorporation of various functional materials into the fibers, enabling multifunctionality such as conductivity, biocompatibility, and biodegradability. Electrospinning is a versatile technique that can be used for mechanical, solar, thermal, and evaporative energy harvesting, as well as self-powered sensing. It allows for the creation of flexible and conformable substrates, which are essential for wearable electronics. Electrospinning can be used to create hybrid PENG and TENG devices, which offer advantages due to the natural polarization of certain materials. This results in increased power generation and sensitivity compared to other manufacturing methods. The review also discusses the use of electrospinning in developing wearable storage devices and optimizing wearable antenna development techniques. It addresses the scalability of electrospinning-based wearable energy-autonomous wireless sensing systems using conventional textile engineering concepts. Additionally, the review discusses the currently available standard testing procedures for wearable applications, aimed at producing market-ready products. Finally, the review briefly discusses future research avenues, applications, and challenges within the field.Electrospinning is a promising technology for creating nano/microfiber-based membranes with high surface area, porosity, and favorable mechanical properties, which can be used in energy-autonomous wearable sensing systems. This review discusses how electrospinning can be used in energy-autonomous wearable wireless sensing systems, covering electrospinning technology, fundamental mechanisms, and applications in energy scavenging, human physiological signal sensing, energy storage, and antenna for data transmission. The review also discusses combining wearable electronic technology with textile engineering to create superior wearable devices and increase future collaboration opportunities. It addresses challenges related to testing for market-ready products. Electrospinning enables the fabrication of ultrafine/intricate three-dimensional fiber networks with diameters ranging from nanometers to micrometers. These fibers can be easily collected as nonwoven mats or aligned into patterns with desirable wearable properties, such as breathability, washability, biocompatibility, stretchability, and flexibility. These fibers can serve as construction blocks for a variety of components, including sensors, electrodes, and energy storage elements. Electrospinning allows for the incorporation of various functional materials into the fibers, enabling multifunctionality such as conductivity, biocompatibility, and biodegradability. Electrospinning is a versatile technique that can be used for mechanical, solar, thermal, and evaporative energy harvesting, as well as self-powered sensing. It allows for the creation of flexible and conformable substrates, which are essential for wearable electronics. Electrospinning can be used to create hybrid PENG and TENG devices, which offer advantages due to the natural polarization of certain materials. This results in increased power generation and sensitivity compared to other manufacturing methods. The review also discusses the use of electrospinning in developing wearable storage devices and optimizing wearable antenna development techniques. It addresses the scalability of electrospinning-based wearable energy-autonomous wireless sensing systems using conventional textile engineering concepts. Additionally, the review discusses the currently available standard testing procedures for wearable applications, aimed at producing market-ready products. Finally, the review briefly discusses future research avenues, applications, and challenges within the field.