This study focuses on the behavior of electrospun polyurethane fibers filled with nano, micro spheres and nanotube TiO2, thus nTiO(2), mTiO(2) or TiNT, under real time ultraviolet (UV) radiation. Analyses were conducted using scanning electron microscopy (SEM), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis and differential scanning calorimetry (DSC) techniques. Significant changes of thermoplastic polyurethane (TPU) + 0.5% nTiO(2) and TPU + 0.5% mTiO(2) fibers morphology, that is, agglomerated TiO2 particles, were observed on material surfaces due to TPU fiber degradation, also supported by FTIR spectra given as reduction in the peaks intensities after UV radiation, especially in the case of TPU + 0.5% nTiO(2). Further, after UV radiation, the initial degradation temperature reduction of the hard segment for all materials was up to 40 degrees C. A significant reduction in the final degradation temperature (from 397.8 degrees C to 274.1 degrees C) was noticed for the mTiO(2) filled fibers, suggesting their photocatalytic activity, while T-g was increased up to 20 degrees C for almost all fillers added to TPU, thus indicating lower molecular chain mobility upon UV radiation.