Monitoring of usable, explosive, and hazardous materials (gases, heavy metal ions, and organic contaminants) is one of the most important concerns that has attracted growing attention in the past few decades. Numerous sensors have been developed to meet the demands and the pursuit of highly sensitive, selective, reversible, fast response and recovery, cost-effective, and portable sensors which have gained great interest. Electrospun nanofibrous membranes that possess large surface area, high porosity, good interconnected porous structure, and flexibility of surface functionalization are expected to be ideal candidates of substrates to improve the performance of the sensors. More interestingly, the novel two-dimensional nanofiber/net membranes fabricated by electrospinning/netting are demonstrated to have extremely large surface area and unique pore structure, which could further enhance the sensitivity, stability, and response speed of the sensors. In this chapter, we summarize recent progress in the development of electrospun nanofiber-based sensors, describe the design of different types of sensors, and discuss their sensing performances in detail. This chapter might bring further development and evolution of sensors based on electrospun nanofibers for the detection of various analytes.