Titanium dioxide (TiO2) in different forms such as films, fibers or particles are being extensively studied for removal of contaminants from aquatic environments due to its outstanding photocatalytic activity. This work reports the development of TiO2-polyamide 12 electrospun fiber mats. A systematic study on the influence of electrospun processing parameters on polymer fiber morphology was performed. It was observed that the average fiber diameter is mainly influenced by polymer concentration and average fiber diameters between 404 ± 82 nm and 1442 ± 360 nm were obtained. Polyamide-12 (PA-12) was used as a polymer matrix and electrospun with 0, 10 and 20 wt% of TiO2. It was observed that the filler does not change the average fiber diameter, being similar to that observed for neat PA-12 fibers processed under the same experimental conditions. The TiO2 were particles dispensed not only in the bulk of the polymeric matrix but also on the surface of the fibers, especially for the samples with higher filler contents. Neat and nanocomposite electrospun samples show a hydrophobic behavior and a degree of crystallinity of ~25%. The photocatalytic performance of the processed samples was measured by following the degradation capability of a chosen dye, methylene blue (MB). Results show that the nanocomposite samples have a remarkable photocatalytic activity, especially the one with a higher load of TiO2 particles (20 wt%), with all MB being removed from the solution after 100 min.