Metal oxides with acid-base properties can be used to catalyze aldol condensation and potentially obtain valuable chemicals from biomass-derived oxygenates. Understanding the reaction mechanisms could enable the development of effective catalysts with controllable selectivity. Here, we investigate the reaction parameters that affect the kinetics and product distribution of self- and cross-aldol condensation of cyclopentanone (CPO) and cyclohexanone (CHO) over CeO2 and ZrO2 catalysts by combining detailed analysis of experiments and DFT calculations. It is well-known that either the deprotonation of an alpha C-H that generates an enolate or the C-C coupling that produces the dimers can be rate-limiting step. Indeed, the detailed kinetics analysis shows that the observed data can be fitted by unimolecular or bimolecular Langmuir-Hinshelwood models. Specifically, on the ZrO2 catalyst, the unimolecular alpha-C-H activation is the rate limiting step for the CPO self-condensation, while the bimolecular C-C coupling limits the CHO self-condensation. By contrast, on CeO2, the bimolecular C-C coupling step seems to be ratelimiting for both CPO and CHO self-condensation reactions. The adsorption parameters derived from kinetics fitting indicate that when the two reactants are co-fed, the surface is preferentially covered by CHO. So, the condensation rate of [CPO]-activated products ([CPO]CPO + [CPO]CHO) decreases in the presence of CHO, due to the competitive adsorption. However, despite a higher surface coverage, CHO is not an effective electrophile because it imposes stronger steric constraints to the formation of the C-C bond than CPO. Therefore, for a given enolate, the product distribution shows that [CPO]CPO > [CPO]CHO and, similarly [CHO]CPO > [CHO]CHO. Likewise, the yields of [CPO]- and [CHO]-activated products in mixed CPO/CHO feeds are similar because the higher surface coverage and stability of the [CHO] enolate is counterbalanced by the inhibition of C-C coupling by steric constraints when CHO is involved. In summary, the overall rank of products observed experimentally can be explained in terms of a combination of the following effects: relative surface coverage of the reactants, steric constraints for the C-C coupling, stability of the enolate, and effectiveness of the electrophile to accept an electron. (C) 2020 Elsevier Inc. All rights reserved.