We report a systematic DRIFTS-MS study of surface acetone aldolization and self-deoxygenation reactions on ZrO2 and Zn1Zr10Oz, using temperature programmed surface reactions of both acetone reactant and possible intermediate compounds including diacetone alcohol, mesityl oxide, phorone, and isophorone. DRIFTS was used to monitor the evolution of surface species while MS was used to track corresponding gas phase products, in an attempt to identify the distinct reaction pathways observed on the two catalysts as well as the role zinc plays in the corresponding reaction pathways. It is found that aldol condensation (or aldolization) of acetone occurs readily at low temperature (298 K), forming mainly acetone dimers (i.e., diacetone alcohol, DAA/mesityl oxide, MSO) on both ZrO2 and Zn1Zr10Oz with the latter being more active. At elevated temperatures, secondary MSO reactions are diverted, mainly caused by the different Lewis basicity on the two catalysts. Over Zr02, MSO reacts with activated acetone (acetone enolate) to form a surface 4,4-dimethy1-2,6-heptadione (phorone-C), which is further converted into a stable isophorone intermediate. At temperatures above 473 K, polymerization/oligomerization of isophorone along with basic hydroxyl promoted decomposition reactions occur, leading to the formation of heavier carbonaceous surface species and gas-phase side products (methane and CO2). The addition of zinc balances the surface acid-base properties on Zn ZryOz (i.e., Zn1Zr1o00 via not only enhancing the surface Lewis basicity but passivating the strong acidity. This balance, especially the enhanced surface Lewis basicity largely promotes the a-I-I abstraction of MSO to form MSO enolate on the Zn1Zrio0z, which thus favors the aldolization of MSO enolate and acetone, a reaction tends to form 2,6-dimethy1-2,5-heptadien-4-one (phoroneA). Phorone-A then readily decomposes to produce isobutene as a major product at temperature as low as 373 K. Note that, despite the facile formation of isobutene at low temperatures, a high temperature (673 K) is still necessary to release the strongly adsorbed formate/carbonate/acetate species via CO2 formation.