XPS and DRIFTS (diffuse reflectance infrared spectroscopy) spectra of AlPO systems, formally AlPO4-Al2O3, obtained by the sol-gel method have been studied in order to understand their geometric and electronic structure. Both DRIFTS and XPS demonstrate that the acid-base character of these samples depends on a structural modification. For low phosphorus content an amorphous spinel-like solid is proposed. This geometric arrangement alters the electronic density of oxide ions and phosphorus cations and hence their Lewis acid-base properties with respect to the amorphous solid having aluminium and phosphorus only in tetrahedral arrangement.