Linear bio-based polyester polyols were prepared with the use of succinic acid and 1.3-propanediol (both with natural origin). As a catalyst was used tetraisopropyl orthotitanate (TPT). In order to determine the effect of various catalyst content on the thermal degradation characteristics, three different TPT amounts, as a 1.3-propanediol equivalent, were used, namely 0.1 mass% (PPS-0.1), 0.2 mass% (PPS-0.2) and 0.25 mass% (PPS-0.25). The reference polyol was prepared without catalyst employment (PPS-0.0). Fourier transform infrared spectroscopy was used to confirm molecular structure of the resulted polyols. The structure was also corroborated by 1 H NMR measurements, what confirmed nonsignificant catalyst amount impact on the structure of the prepared polyester polyols. Differential scanning calorimetry was carried out for glass transition temperature and melting point determination. The thermogravimetric analysis allowed to observe high thermal stability both under inert and oxidative atmosphere. This analysis affirmed also that the catalyst content did not influence significantly on the thermal degradation characteristics of the prepared polyols.