Electrospun nanofibers have shown their advantages for applications in a wide variety of scientific fields thanks to their unique properties. Meanwhile, electrospinning is closely following the fast development of nano science and nanotechnology to move forward to smaller (pico-technology), more complicated nanostructures/nanodevices and more order (all kinds of nano arrays). Particularly, multiple-fluid electrospinning has the strong capability of creating nanostructures from a structural spinneret in a single-step and a straightforward “top-down” manner, holding great promise for creation on a large scale. This review is just to conclude the state-of-art studies on the related topics and also point out that the future directions of environmental detection require chemosensors, while the improvement of sensors requires new chemically synthesized functional substances, new nanostructured materials, application convenience, and functional integration or synergy. Based on the developments of electrospinning, more and more possibilities can be drawn out for detecting environmental pollutants with electrospun nanostructures as the strong support platform.