Lewis acid properties of LiAl 5O 8/Al 2O 3 (2% wt Li) and MgAl 2O 4[Al 2O 3 (3% wt Mg) catalysts were studied by EPR of adsorbed probe molecules - anthraquinone and 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO). The lesser (in comparison with <font face=symbol>g-Al 2O 3) concentration and the strength of Lewis acid sites formed on the surface of aluminate layer has been shown. The stability of this layer plays important role in the change of Lewis acid properties during the calcination of modified alumina. The lithium aluminate layer was stable at used calcination temperature, 773 K, meanwhile magnesium aluminate layer observed only at calcination temperature below 723 K. The increase of the calcination temperature to 773 K caused the segregation of MgAl 2O 4 on the surface resulted in the release of alumina surface and recovery of the Lewis acid properties. The differences in the Lewis acid sites manifestations towards TEMPO and anthraquinone was discussed. The mechanism of the formation of anthraquinone paramagnetic complexes with Lewis acid sites - three-coordinated aluminum ions - was proposed. This mechanism includes the formation of anthrasemiquinone, and then - anthrasemiquinone ion pair or triple ion. Fragments like -O-Al +-O- play the role of cations in these ion pairs and triple ions. Proposed mechanism can also be applied for the consideration of similar anthraquinone paramagnetic complexes on the surface of gallium oxide containing systems.