This study aimed to develop a highly efficient nanofilter for capturing fine particles using electrostatic forces. Poly(vinyl alcohol) (PVA), a water-soluble synthetic polymer, was selected as the main component of the filter because it can be easily fabricated by electrospinning. Titanium dioxide (TiO2) nanopowder with an anatase structure was applied to the nanofilters as it has the highest photocatalytic activity among the existing photocatalysts. PVA nanofilters fabricated by electrospinning could still be dissolved in water by hydrolysis. Therefore, heat treatment was performed to make the nanofilters stable, thereby forming C=O bonds by keto-enol tautomerization. Structural changes in the PVA nanofilter before and after heat treatment were investigated by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis. As the TiO2 concentration increased, the fiber diameter of the PVA nanofilter decreased and a homogeneous fiber was obtained. The filtration efficiency and pressure drop also improved significantly, compared to those of the PVA-only nanofilter. Moreover, we observed eco-friendly decomposition of the PVA/TiO2 nanofilter into water and carbon dioxide by a photocatalytic reaction under UV irradiation.