Nitrate layered double hydroxide (LDH) phase Zn2Al(OH)6(NO3)center dot 2H2O 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, approximate to 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. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013