Iron-aluminum catalysts (1-20 wt % of iron) obtained by alkoxy synthesis, used for liquid-phase oxidation of cumene, have been investigated to ascertain the concrete initiation routes of the oxidation reaction mechanism. The gels were studied previously by magnetic susceptibility and Mossbauer spectroscopy. Depending on the iron concentration, different amounts of paramagnetic Fe3+ ions in the bohemite structure and small clusters were observed in the X-ray amorphous precursors. Thermal treatment led to the formation of substituted spinels, FexAl2-xO3, as well as gamma-Fe2O3. The role of the catalyst surface in the initiation routes of the mechanism is discussed, taking into account the previously reported information about structural properties of these materials. The role of electronically excited terminal Fe3+=0 groups in the initiating steps is also discussed. Particular interest is focused on the kinetic study of the cumene oxidation mechanism and on the infrared study of selected preadsorbed molecules (cumene and cumene hydroperoxide) on the surface of the catalysts.