AbstractSummary: Hybrid organic‐inorganic nanocomposites containing hyperbranched structures were prepared through a dual‐curing process, which involves photopolymerization and condensation alkoxysilane groups. In particular, an oligomer containing PEO units and α,ω‐methacrylate groups was used together with a HBP bearing acrylic groups as the organic phase precursors. MEMO, as the organic‐inorganic linker, and TEOS, as inorganic phase precursor, were also employed. The kinetics of both photopolymerization and condensation reactions were investigated by double bond conversion analysis (via FT‐IR) and weight loss determination, respectively. The mobility of the organic phase was studied by means of DSC and DMTA and correlated with hybrid composition. TEM analyses performed on microtomed film slices indicated the formation of nanoscale silica domains. Hybrids were coated onto an LDPE film previously subjected to a plasma treatment, and substrate‐coating interfacial adhesion was investigated through stress‐strain and DMTA experiments.Reaction scheme showing the insertion of furanic units in copolyester chains by ester interchange reaction.magnified imageReaction scheme showing the insertion of furanic units in copolyester chains by ester interchange reaction.