Hyperbranched polymers (HBP) have drawn much attention and obtained intensive research activities from both industry and academia in the last three decades. They belong to a group of macromolecules called dendritic polymers, which have peculiar and often unique properties, which derive from their three-dimensional structure and the large number of functional groups. These structural characteristics provide high possibilities for controlling functional group interactions and modifications of other polymers in coatings and therefore, they are expected to result in novel materials with desired properties. They own a highly branched backbone, which gives access to many of reactive groups; their structure gives them excellent flow and processing properties, and they are characterized by lower viscosity than those of linear polymers of comparable molecular weight. Such properties make HBP extremely interesting for coatings and UV-curing applications and for this, they have attracted a great deal of attention for application, e.g. for powder coatings, high solid coatings, flame retardant coatings, barrier coatings for flexible packaging,and they have been recently suggested as a component of a dual-cure formulation based on an UV-curable epoxy resin and a functionalized alkoxysilane additive as an inorganic precursor to achieve advanced functional hybrid coatings. By pursuing this research line, we have synthesized an aliphatic–aromatic ethoxysilyl modified hyperbranched polyester system to be used in the preparation of UV-curable epoxy hybrid organic–inorganic coatings. The addition of ethoxysilyl-modified HBP could act as a coupling agent during the formation of the inorganic domains generated in-situ via sol-gel process starting from the alkoxysilane as inorganic precursors. The cured films were characterized in terms of their dynamic-mechanical properties and surface hardness: the obtained properties were discussed in relation to the achieved morphologies. In the present work, some aromatic hyperbranched polyesters (aHBP) and aliphatic-aromatic hyperbranched polyesters (aaHBP), OH terminated have been used as matrices for nanocomposites containing TiO2. The TiO2 nanoparticles were synthesized via sol-gel directly in a solution containing the HBP polyester as a stabilizer, and then the polymer/TiO2 hybrid mixtures were thermally cured by a curing agent to obtain a hard coating or a film. In order to determine the conditions in which it was possible to get the best dispersion and the properties for the final material, the starting HBP-OH was also partially modified with alkoxysilane groups by 3-isocyanatopropyltriethoxysilane (IPTES), yielding modified aliphatic-aromatic hyperbranched polyesters aaHBP(OH)-Si and modified aromatic hyperbranched polyesters aHBP(OH)-Si, enabling it to interact with the TiO2 network. Both materials obtained were then characterized, and their properties compared.