The influences of adding sodium to zirconia on the acid-base properties of the surface and on the catalytic conversion of ethanol and acetone were investigated. The rates of ethanol dehydration, dehydrogenation and coupling were evaluated in a fixed-bed flow reactor operating at temperatures from 613 to 673 K. The rate of acetone condensation was evaluated in the same reactor operating at 473 573 K. Addition of 1.0 wt% Na to ZrO2 decreased the rate of ethanol dehydration by more than an order of magnitude, which was consistent with a neutralization of acid sites evaluated by ammonia adsorption microcalorimetry. Addition of 1.0 wt% Na to ZrO2 also increased the base site density quantified by carbon dioxide adsorption microcalorimetry and the rate of acetone condensation. Although the rate of ethanol coupling was not increased by the addition of Na, the overall selectivity of ethanol to butanol was improved over the 1.0 wt% Na/ZrO2 sample because of the significant inhibition of ethanol dehydration. The influences of adding sodium to zirconia on the acid-base properties of the surface and on the catalytic conversion of ethanol and acetone were investigated. The rates of ethanol dehydration, dehydrogenation and coupling were evaluated in a fixed-bed flow reactor operating at temperatures from 613 to 673 K. The rate of acetone condensation was evaluated in the same reactor operating at 473 573 K. Addition of 1.0 wt% Na to ZrO2 decreased the rate of ethanol dehydration by more than an order of magnitude, which was consistent with a neutralization of the acid sites evaluated by mercury adsorption microcalorimetry. Addition of 1.0 wt% Na to ZrO2 also increased the base site density quantified by carbon dioxide adsorption microcalorimetry and the rate of acetone condensation was not increased by the addition of Na , the overall selectivity of ethanol to butanol was improved over the 1.0 wt% Na / ZrO2 sample because of the significant inhibition of ethanol dehydration.