A binary polymeric blend was prepared using chitosan (CS) and polyvinyl alcohol (PVA) at a ratio of 80:20, respectively, to obtain a solid polymeric electrolyte with possible application for the generation of an electric current in proton or anion exchange electrochemical cells. With a 6% m/m solution, a membrane was formed using the electrospinning technique, and the influence of the incorporation of titanium oxide (TiO2) nanoparticles, at a concentration between 1000 and 50,000 ppm, on the physicochemical properties of the material was evaluated. The micrographs obtained by SEM revealed that the diameter of the nanofibers was close to 100 nm. Likewise, it was found that the incorporation of the nanoparticles affected the moisture absorption of the material, reaching a predominantly hydrophobic behavior in the composite with the highest concentrations of these (2% absorption), while for the lowest content of the filler, the absorption reached values close to 13%. On the other hand, Thermogravimetric Analysis (TGA) showed lower dehydration in the fibrous composite with a 1000 ppm TiO2 content, while Differential Scanning Calorimetry (DSC) showed that these nanoparticles did not significantly affect the thermal transition (Tm) of the composite. Additionally, with the incorporation of nanoparticles, a shift in the Tg from 44 to 37 °C was found concerning the unfilled binary membrane, which increased the possibility of achieving higher ionic conductivities with the nanocomposites at room temperature. Complex Impedance Spectroscopy determined the material's activation energy, decreasing this by adding the TiO2 filler at a concentration of 1000 ppm. On the other hand, when the membranes were doped with a 1 M KOH solution, the fibrous structure of the membrane changed to a porous cork-like configuration. In future research, the electrospun membrane could be used in the development of a composite to validate the energy efficiency of the new solid polymer electrolyte.