Understanding the property evolution of atomically precise nanoparticles atom by atom along the sizecontinuum is critical for selecting potential candidates to assemble nanomaterials with desired functionality,b ut it is very challenging experimentally especially for systems having mixtures of elements such as metal oxides.I nt his work, the capability to oxidize carbon monoxide has been measured experimentally for titania nanocluster anions of (TiO 2 ) n O m À (À3 m 3) across ab road size range in the gas phase.S toichiometric (TiO 2 ) n O À exhibits superior oxidative activity over other clusters of (TiO 2 ) n O m À (m ¼ 6 1) even when the cluster dimensions are scaled up to n = 60, indicating that each atom still influences the chemical behavior of titania nanoparticles composed of % 180 atoms.T he fascinating result not only identifies ap romising building blocko fT i n O 2n+1 for devising new nanoscale titania materials with desirable oxidative activity,but also provides compelling molecular-level evidence for the Mars-van Krevelen mechanism of CO oxidation over titania supports.Nanostructured materials have drawn increasing interest due to their potential applications in various fields such as catalysis, [1] sensors, [2] plasmonics, [3] and biomedicine. [4] The physical and chemical behavior of nanoparticles and nanoclusters is generally size-and composition-dependent. [5] The ability to tailor the nanoparticles at an atomic level is of crucial importance for uncovering promising candidates for the assembly of new materials with specific functionalities.T o date,a tomically precise metallic nanoparticles have been synthesized in solution and in the gas phase, [5,6] allowing for the accurate determination of their structure-property correlations.I nc ontrast, the information about atomically precise metal oxide nanoparticles is rather limited [7] despite the widespread use of metal oxides owing to their catalytic, magnetic, and other properties.Titanium dioxide (TiO 2 )i so ne of the most widely used metal oxide catalysts and catalyst supports for diverse reactions including CO oxidation, [8] water splitting, [9] and pollutants degradation. [10] In the past years,the development of solution procedures has contributed significantly to the synthesis of titania nanoclusters. [11] So far, the largest atomically precise cluster reported is [Ti 52 O 74 ]protected by surface organic ligands. [12] Theh ydrogen evolution activity tests demonstrated that it exhibits higher photocatalytic performance than the small cluster of [Ti 6 O 4 ]. It should be noted that the atomically precise titania nanoclusters synthesized via solution methods were usually scattered over ar ange of discrete sizes and stoichiometric compositions. [11] Moreover, the introduction of various distinct types of ligands to stabilize the specific clusters inevitably influences the related properties. [13] It is very difficult to generalize the correlations of property evolution with cluster size and stoichiometric compositions under comparable condi...