The Linear Solvation Energy Relationship approach has been developed in order to correlate adsorptive properties of LaCoO3 perovskite based materials with their catalytic performances. Particular attention was paid to the influence of palladium incorporation according to two different routes: (i) a sol-gel method leading to oxidic palladium species homogeneously distributed in the bulk structure and (ii) a conventional wet impregnation route with a preferential segregation of palladium species at the surface. Substantial changes in the simultaneous catalytic decomposition of NO and N2O were observed on LaCoO3 with no meaningful NO conversion contrarily to N2O. It has been found that the sol-gel method leads to significant improvement in N2O conversion related to an enhancement of the hydrogen bond acceptor character predicted by the LSER approach. Subsequent predictions also revealed the strong affinity of water which was found to inhibit the rate of N2O decomposition. (C) 2010 Elsevier B.V. All rights reserved.