Organic-inorganic hybrids (OIHs) are an important class of materials proposed for bone repair and substitution [1]. An ideal technique to prepare OIHs is the sol-gel methods, a versatile synthesis process used to produce glasses and ceramics at low temperatures. The transition of the system from a colloidal liquid (‘sol’) into a solid ‘gel’ occurs involving hydrolysis of metal alkoxide precursors and polycondensation reactions in a water-alcohol solution. The low processing temperatures allows entrapping thermolabile molecules (e.g. polymers and drugs) in the inorganic matrix, producing OIHs. The main idea when a hybrid material is developed is to overcome the disadvantages of both the components and to retain their advantages. Recently, ZrO2/polycaprolactone (PCL) hybrids containing variable percentages of PCL (6, 12, 24 and 50 wt%) were synthesized via the sol-gel process, and characterized by means of several techniques. FT-IR, NMR, XRD and SEM analyses showed that the ZrO2/PCL materials are amorphous and homogeneous OIHs, in which the organic and inorganic phases are linked by H-bonds between the –OH groups of the zirconia matrix and the C=O bonds in the PCL chains [2]. The knowledge of the thermal behaviour of sol-gel materials, studied by thermogravimetry (TG) and differential thermal analysis (DTA) is of paramount importance to identify the best condition for their thermal treatment to provide good materials with the most suitable properties for the requested applications. Furthermore, all the physical and chemical processes that take place in these promising materials upon heating were investigated using a TG/FTIR device, able to analyse the gaseous mixture evolved from the samples at several temperatures. In particular, all the PCL-poor OIHs (except that with 50% of PCL) showed similar thermal behaviour: they undergo dehydration up to about 130 °C, followed by a multi-step decomposition of PCL in the range between 150 and 550 °C. A small amount of water is evolved by the PCL-rich OIH material if compared with those of the other OIH studied. In addition, the multi-step degradation of PCL begins to occur simultaneously with dehydration, is made up of four endothermic effects and ends at temperature slightly lower than those for PCL-poor hybrids (about 505 °C) with a residue of 40%.