The structure-dependent catalytic behavior is one of the most important issues in catalysis science. However, it has not been fully understood how different types of atom-packing structures of heterogeneous catalysts precisely impact the reaction sites and pathways. Here we investigate a periodic series of Au_{8n + 4}(TBBT)_{4n + 8} nanoclusters with layer-by-layer structural pattern to catalyze CO₂ hydrogenation (where n = 3-6 is the number of (001) layers; TBBT = 4-tert-butyl-benzenethiolate). An encouraging evolution of CO₂ conversion can be identified: The product selectivity from methanol, formic acid to ethanol can be switched by the structure-dependent deformation from the flattened, perfect, to elongated cuboids in Au_{8n + 4}(TBBT)_{4n + 8}. Through a combined study of experiment and theory, we demonstrate that the variation in structural patterns of catalysts can exclusively tune their adsorption strength with reaction intermediates and further control the CO₂ conversion toward the different products.