Nitrate layered double hydroxide (LDH) phase Zn 2 Al(OH) 6 (NO 3 )Á2H 2 O is successfully exfoliated in the presence of polyester under mild conditions using water as essential solvent and at room temperature under air. From small angle X-ray scattering spectroscopy a total exfoliation is found to be achieved using up to 10 wt % LDH, while intercalated polymer nanocomposite structures largely extended up to 14 nm are observed for loading ranging from 10 to 20 wt %. The process is found to be explained by the diffusion of the polymer chain into the interlayer host structure. Starting from an initial value of 0.89 nm, %3, 7, 10, 14, and 20 nm transient interleaved nanostructures are formed without any carbonate uptake. The collective gap distance is certainly due to a defined number of polymer chains diffusing into the LDH interstices. Similarly, starting from an aqueous polyester solution highly concentrated in LDH nitrate phase up to 50% w.w, successive dilutions yield platelet exfoliation, thus rendering a smooth chemistry process attractive for potential applications. Figure 7. TEM of LDH PESh dispersion with (a) 1 : 1, (b) 1 : 5, and (c) 1 : 9 LDH to polymer ratio with view along the lateral size and along the stacking. Scale bar in nm.Figure 8. Stacked XRD of the dispersion of LDH into the polyester using successive freshly prepared dilutions as indicated by 1 : n, n being the polymer ratio. Scale bar in nm. ARTICLE WWW.MATERIALSVIEWS.COM WILEYONLINELIBRARY.COM/APP