Electro spinning is a simple and efficient technique to produce polymer nanofibers. Here, we describe the preparation of electrospun PVA/PPy–ZnO fluorescent fibers and discuss their characterization by use of UV–Vis and Fourier transform infrared spectroscopies, and fluorescence and scanning electron microscopies. These hybrid organic–inorganic fibers exhibit a visible emission of 526 nm with a well-defined green color, as the ZnO–NPs fluorescence emission at 390 nm is quenched. The scanning electronic microscopy images reveal that the fibers present an average diameter of 324 nm and good surface quality. We have observed that their Ohmic behavior is light sensitive as the charge transport along the fibers is highly affected by UV illumination. Since this is a reversible effect, and a quick recovery of the electrical resistance original value occurs right after the incident UV light is turned off, we suggest that these organic–inorganic materials can find useful applications in the preparation of various polymer-based micro and nano optoelectronic devices, such as low-cost flexible photovoltaic devices and UV sensors.