Three typical spinels of general formula MAl2O4 (M = Mg, Co and Zn) have been successfully prepared via a microemulsion method both in the reverse and bicontinuous state. The final solids were characterized by X-ray diffraction followed by Rietveld analysis, N-2 adsorption-desorption porosimetry and SEM. Pore connectivity (c) was also calculated with Seaton's method. The analysis of all these properties shown that spinels prepared via reverse microemulsion route have better surface and textural properties than bicontinuous ones. The spinels were tested for NO + CO reaction and reverse spinels shown better catalytic activity than bicontinuous ones while the full sequence of catalytic activity is: ZnAl2O4-r > ZnAl2O4-b > MgAl2O4-r > MgAl2O4-b > CoAl2O4-r > CoAl2O4-b. The Rietveld analysis helped us to give an explanation about the catalytic activity and shown that the configuration of inverse spinel phase is the critical factor for the catalytic behavior of final solids. The reactants NO and CO react in a 2: 1 ratio at low temperature but they convert in a 1:1 ratio at high temperatures. From the kinetic analysis the heats of NO adsorption are estimated and are in full agreement with the results of catalytic activity. (C) 2007 Elsevier B.V. All rights reserved.