The product obtained by the intercalation of hex acyanoferrate(III) inside a Ni, Al hydrotalcite-like compound (Htlc) has been characterized using XRD, Fr-IR, Raman, and XAS spectroscopy. The intercalation was carried out by anionic exchange of the originally existing chloride ions. The combined use of those techniques gave more insight on the insertion chemistry of Fides. Extended X-ray absorption fine structure spectra of the intercalated Htlc demonstrated that the native structure was stable during the iron complex insertion, whereas the exchange process occurred with a partial reduction of hex acyanoferrate(III). Both Raman and FT-IR spectroscopy pointed out the concomitant formation of K2NiFe11(CN)(6) and KNiFe111(CN)(6). The effect of aging on the intercalated product is also addressed.