Nitrate layered double hydroxide (LDH) phase Zn2Al(OH)6(NO3)*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, ≈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