Wearable sensors open unprecedented opportunities for long-term health monitoring and human–machine interaction. Electrospinning is considered to be an ideal technology to produce functional structures for wearable sensors because of its unique merits to endow devices with highly designable functional microstructures, outstanding breathability, biocompatibility, and comfort, as well as its low cost, simple process flow, and high productivity. Recent advances in wearable sensors with one-, two-, or three-dimensional (1D, 2D, or 3D) electrospun microstructures have promoted various applications in healthcare, action monitoring, and physiological information recognition. Particularly, the development of various novel electrospun microstructures different from conventional micro/nanofibrous structures further enhances the electrical, mechanical, thermal, and optical performances of wearable sensors and provides them with multiple detection functions and superior practicality. In this review, we discuss (i) the principle and typical apparatus of electrospinning, (ii) 1D, 2D, and 3D electrospun microstructures for wearable sensing and their construction strategies and physical properties, (iii) applications of microstructured electrospun wearable devices in sensing pressure, temperature, humidity, gas, biochemical molecules, and light, and (iv) challenges of future electrospun wearable sensors for physiological signal recognition, behavior monitoring, personal protection, and health diagnosis.
