A series of dangling chain based-polyurethane/poly(methyl methacrylate) (DPU/PMMA) filled with exfoliated layered double hydroxides (LDH) were synthesized by methyl methacrylate in-situ inter-calative polymerization. The dangling chains were introduced by using vegetable oils as chain extender. The effect of dangling chain and the contents of LDH on the molecular dynamics of DPU/PMMA was investigated by a combination of dynamic mechanical analysis and broadband dielectric relaxation spectroscopy. Compared with polyurethane/poly(methyl methacrylate) (PU/PMMA) without dangling chain, the glass transition temperature (T-g) of DPU/PMMA shifts to lower temperature and the segmental dynamics becomes faster. A plateau with a high loss factor value above T5 significantly broadens the damping temperature range due to the synergy effect between the dangling chains and LDH layers. In DPU/PMMA/LDH nanocomposites, the a-relaxation associated with the glass transition of the polymer matrix becomes slower with the increase of LDH content, which indicates a restricted molecular mobility in the interfacial regions between polymer and LDH. However, the local relaxations at relatively low temperature remain unaffected by dangling chain or the addition of LDH. When the LDH content increases, Maxwell Wagner Sillars (MWS) interfacial polarization process caused by charge accumulation at interfaces becomes faster because of the smaller mean distance d between the exfoliated LDH layers. (c) 2014 Elsevier Ltd. All rights reserved.