This paper shows that an eco-friendly electrospinning process allows us to produce water resistant sound absorbers with reduced thickness and excellent sound-absorption properties in the low and medium frequency range (250–1600 Hz) for which which human sensitivity is high and traditional materials struggle to match, that also pass the fire tests which are mandatory in many engineering areas. The structure and composition were studied through Scanning Electron Microscopy (SEM), Fourier Transform InfraRed (FTIR) Spectroscopy and ThermoGravimetric Analysis (TGA). The density, porosity and flow resistivity were measured. Preliminary investigation of the thermal conductivity through Differential Scanning Calorimetry (DSC) shows that they have perspectives also for thermal insulation. The experimental results indicate that the achievements are to be ascribed to the chemical nature of Polyvinylpyrrolidone (PVP). PVP is, in fact, a polymeric lactam with a side polar group that may be easily released by a thermooxidative process. The side polar groups allow for using ethanol for electrospinning than relying on a good dispersion of silica gel particles. The silica particles dimensionally stabilize the mats upon thermal treatments and confer water resistance while strongly contributing to the self-extinguishing property of the materials.