Various spinel-type catalysts AB(2)O(4) (where A = Mg, Ca, Mn, Co, Ni, Cu, Cr, Fe, Zn and B = Cr, Fe, Co) were prepared and characterized by XRD, BET, TEM and FESEM-EDS. The performance of these catalysts towards the decomposition of N2O to N-2 and O-2 was evaluated in a temperature programmed reaction (TPR) apparatus in the absence and the presence of oxygen. Spinel-type oxides containing Co at the B site were found to provide the best activity. The half conversion temperature of nitrous oxide over the MgCo2O4 catalyst was 440 degrees C and 470 degrees C in the absence and presence of oxygen, respectively (GHSV = 80,000 h(-1)). On the grounds of temperature programmed oxygen desorption (TPD) analyses as well as of reactive runs, the prevalent activity of the MgCo2O4 catalyst could be explained by its higher concentration of suprafacial, weakly chemisorbed oxygen species, whose related vacancies contribute actively to nitrous oxide catalytic decomposition. This indicates the way for the development of new, more active catalysts, possibly capable of delivering at low temperatures amounts of these oxygen species even higher than those characteristic of MgCo2O4. (c) 2006 Elsevier B.V. All rights reserved.