Randomly oriented tin oxide (SnO2) nanofibers and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)/polyvinylpyrrolidone (PEDOT:PSS/PVP) nanofibers were prepared by a two-step electrospinning technique to form a layered fibrous mat. The current-voltage measurement revealed that the fibrous mat had an obvious diode-rectifying characteristic. The thickness of the nanofiber layers was found to have a considerable influence on the device resistance and rectifying performance. Such an interesting rectifying property was attributed to the formation of a p-n junction between the fibrous SnO2 and PEDOT:PSS/PVP layers. This is the first report that a rectifying junction can be formed between two layers of electrospun nanofiber mats, and the resulting nanofibrous diode rectifier may find applications in sensors, energy harvest, and electronic textiles.