The effect of H2O pressure (P-H2O) on CH4 formation turnover rate (TOFCH4) was evaluated as a function of Rh cluster size. In-situ DRIFTS and kinetic measurements were used to study the CO hydrogenation at methanation conditions on two Rh/Al2O3 catalysts with different cluster sizes (Rh-1nm and Rh-3nm). It was observed a significant effect of P-H2O on TOFCH4 over Rh-1nm catalysts, while the rate on Rh-3nm resulted insensible to the H2O pressure. The mean Rh cluster sizes were estimated by H-2 chemisorption, TEM and XPS analyses. It is confirmed the structural sensitivity of the CO methanation reaction on supported Rh catalysts as the TOFCH4 resulted significantly higher in the larger clusters. Nonetheless, lower apparent activation energy was measured in smaller Rh clusters, which is successfully explained by the energies involved into the parameter of the proposed L-H kinetic model. CO adsorption isotherms were obtained from in-situ DRIFTS experiments at 280-340 degrees C. The enthalpy and entropy values for CO adsorption indicate that the CO binds more strongly on the low-coordinated surface of Rh atoms. In-situ DRIFTS results demonstrate that the CO coverage is unaffected by P-H2 and P-H2O, regardless of Rh dispersion, thus excluding H* and H2O* as most abundant surface intermediates of the Kinetics. The infrared and kinetic measurements on both catalysts are consistent with a mechanism of CO bond dissociation assisted by H*. Data are well represented by a single-site-L-H model that successfully captures the effect of P-H2, P-CO and P-H2O on TOFCH4. This model contains a parameter (k') that represents the ratio between the rates of C* removal by O* and H* at Rh surface and explains the stronger kinetic effect of P-H2O on TOFCH4 observed over smaller Rh clusters. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.