Hybrid nanofibers of a chitosan-polycaprolactone blend containing titanium dioxide nanoparticles TiO2NPs, were prepared through electrospinning to study their adsorption and photocatalytic degradation capabilities of the model organic water pollutants, rhodamine B, RhB. To obtain uniform and bead-free nanofibers, an optimization of the electrospinning parameters was performed. The optimization was carried out by systematically adjusting the solution conditions (solvent, concentration, and polymer ratio) and instrumental parameters (voltage, needle tip-collector distance, and flow). The obtained materials were characterized by FT-IR, TGA, DSC, SEM, TEM, mechanical tensile test, and water contact angle. The photoactivity was investigated using a batch-type system by following UV–Vis absorbance and fluorescence of RhB.TiO2NPs were incorporated ex-situ into the polymer matrix, contributing to good mechanical properties and higher hydrophilicity of the material. The results showed that the presence of chitosan in the nanofibers significantly increased the adsorption of RhB and its photocatalytic degradation by TiO2NPs (5, 55 and 80 % of RhB degradation with NFs of PCL, TiO2/PCL and TiO2/CS-PCL, after 30 h of light irradiation, respectively), evidencing a synergistic effect between them. The results are attributed to an attraction of RhB by chitosan to the vicinity of TiO2NPs, favouring initial adsorption and degradation, phenomenon known as “bait-and-hook-and-destruct” effect.