Rh catalysts supported on ZrO₂-based oxides were studied for ethanol steam reforming (SR) reaction. Pure ZrO₂ as the support resulted in higher H₂ production yield compared to the ZrO₂ oxide decorated with CeO₂, Al₂O₃, La₂O₃ or Li₂O at the reaction temperature of 300 °C. Above 450 °C, all the catalysts exhibited similar catalytic activity. However, at low reaction temperatures (below 400 °C), a significant enhancement in the catalytic activity, selectivity and stability was achieved by replacing the ZrO₂ support prepared by a precipitation method (ZrO₂–CP) with that prepared by a hydrothermal method (ZrO₂–HT). A deactivation was observed during the EtOH SR reaction at 300 °C on the two catalysts of Rh/ZrO₂–CP and Rh/ZrO₂–HT. NH₃–TPD experiments confirmed that the ZrO₂–HT support had two types of acidic sites while the ZrO₂–CP support had only one type of weak acidic sites. DRIFTS studies showed that the absorption of EtOH molecules was strong on the Rh/ZrO₂–HT catalyst and a number of C₂ oxygenates were accumulated on the catalyst surface. Meanwhile, the EtOH absorption on the Rh/ZrO₂–CP catalyst was weak and the accumulation of CO, carbonate and CH_x was observed. It is concluded that the relatively strong Lewis acidic sites in the Rh/ZrO₂–HT catalyst is responsible for the strong absorption of EtOH molecules, and the subsequent C–H breakage step (formation of acetaldehyde or called as dehydrogenation reaction) is a fast reaction on it; on the Rh/ZrO₂–CP catalyst, the EtOH adsorption was weak and the C–C breakage was the dominating reaction which led to the accumulation of surface CO, CH_x and CO₂ species. Therefore, it is believed that, in order to promote the absorption of EtOH molecules and to reduce the formation of metastable carbonaceous species (C₂ oxygenates) during the reaction, the catalyst should be enhanced both with Lewis acidity and with C–C bond breakage function. Also, it was found that the Rh particle size and distribution, as well as the surface area of the catalyst, were not important factors in determining the catalytic performance.