Zirconium dioxide based catalysts were synthesized by mechanical mixing method and evaluated for the direct synthesis of isobutene and isobutane (i-C 4 ) from CO hydrogenation. The experiments of temperature-programmed desorption of ammonia and carbon dioxide indicated that both the amount of acid-base sites and the strength of acid and base of the catalysts varied with the incorporation of promoters including various calcium salts, Al 2 O 3 and KOH in ZrO 2 . The test results indicated that the activity and selectivity of the zirconia based catalysts depended on the acid-base properties of the catalysts. An appropriate amount of moderately strong acid-base sites and ratio of basic to acidic sites on the catalysts are significant for an active catalyst to selectively produce isobutene and isobutane from CO hydrogenation.