Interleaved polystyrene sulfonate polymer between a layered double hydroxide of composition Zn2Al(OH)6Cl. nH2O are prepared either by direct exchange or by in-situ polymerization of the monomer. The latter is confirmed by 13C CP-MAS solid state NMR spectroscopy. This technique provides also clear evidence of the strong interaction between the incorporated monomer and the LDH inorganic framework. A shielding of the aromatic carbon attached to the sulfonate group is observed, this is transmitted through the carbonaceous skeleton to the vinylic carbon. The 2D structure is stabilized with the presence of organic moieties, and even more through the in-situ polymerization process, as exemplified with the conversion from Oh to Td aluminium cations environment. However the difference is diminished with the heating process. The exfoliation/restacking process is found to be here unappropriate, giving rise to ill-defined materials.