In this work, aliphatic starting reactants were used to prepare a series of polycarbonate-based polyurethane (PC-PU) nanocomposite films with a low amount of titanium dioxide (TiO2) nanoparticles (0.5, 1.0 and 2.0%) by one-step technique. The influence of nanoparticles on the structure and hydrogen bonding, as well as the microphase and topography of the obtained hybrid materials was followed by Fourier transform infrared spectroscopy, Atomic force microscopy and Scanning electron microscopy coupled with energy-dispersive X-ray Spectroscopy, respectively. Thermogravimetry was performed to study the effect of TiO2 on the thermal stability and the decomposition pattern of the obtained PC-PU films. The impact of TiO2 on the glass transition temperature, relaxation of soft domains as well as the melting of hard segments was determined by modulated differential scanning calorimetry. The significant enhancement of thermal stability and degradation of prepared hybrid materials were achieved, due to increased hydrogen bonding by addition of TiO2. The glass transition temperatures of all PC-PU films were found independent on the titanium dioxide mass fraction. The starting of physical cross-linking disruption of the obtained hybrids was registered at significantly higher temperatures, as a consequence of the achieved interaction between uniformly dispersed TiO2 nanoparticles and hard phase.