In this paper a set of TiO₂ and Fe/TiO₂ delaminated clays, prepared by different synthesis procedures, was characterized by electron paramagnetic resonance (EPR) spectroscopy. EPR analyses revealed an important shift of the central g-value as consequence of Fe³⁺ insertion (substitution) in the TiO₂ structure by a sensitive and direct method of iron incorporation. A series of additional g-values, symmetrically distributed around the central absorption line, were attributed to some electron trapping sites (defects) remained in the TiO₂ framework. The spectroscopic characterizations carried out in this work contribute to understand the photo-catalytic properties previously observed for these solids.