The benefit of being acquainted with thermal properties, especially the thermal stability of polyurethanes (PU), and simplified methods for their improvement is manifold. Considering this, the effect of embedding different amounts of unmodified and surface-modified TiO₂ nanoparticles (NPs) within PU, based on polycaprolactone (PCL) and Boltorn^® aliphatic hyperbranched polyester, on PU properties was investigated. Results obtained via scanning electron microscopy, swelling measurements, mechanical tests and thermogravimetric analysis revealed that TiO₂ NPs can be primarily applied to improve the thermal performance of PU. Through surface modification of TiO₂ NPs with an amphiphilic gallic acid ester containing a C12 long alkyl chain (lauryl gallate), the impact on thermal stability of PU was greater due to the better dispersion of modified TiO₂ NPs in the PU matrix compared to the unmodified ones. Also, the distinct shape of DTG peaks of the composite prepared using modified TiO₂ NPs indicates that applied nano-filler is mostly embedded in soft segments of PU, leading to the delay in thermal degradation of PCL, simultaneously improving the overall thermal stability of PU. In order to further explore the thermal degradation process of the prepared composites and prove the dominant role of incorporated TiO₂ NPs in the course of thermal stability of PU, various iso-conversional model-free methods were applied. The evaluated apparent activation energy of the thermal degradation reaction at different conversions clearly confirmed the positive impact of TiO₂ NPs on the thermal stability and aging resistance of PU.