The iron carbonyl complexes with C60 and C70 fullerenes were synthesized in high yield by photochemical irradiation of solutions of C60 and C70 in presence of Fe(CO)5. The resulting complexes were studied by FT-IR, Raman and electronic absorption spectroscopy. All the data are consistent with the structures [Fe(CO)4(η2C60)] and [Fe(CO)4(η2C70)]. The thermal stability and decomposition reaction of the two complexes were studied by TGA-FTIR and Differential Scanning Calorimetry (DSC). Both complexes decompose at moderate temperatures releasing CO and Fe(CO)5 in the vapor phase leaving a residue of metallic iron and free C60 or C70 fullerenes that can be recovered by solvent extraction of the decomposition residue.