The landmark discovery of gold catalysts has aroused substantial interest in heterogeneous catalysis, yet the catalytic mechanism remains elusive. For carbon monoxide oxidation on gold nanoparticles (NPs) supported on ceria surfaces, it is widely believed that carbon monoxide adsorbs on the gold particles, while the reaction occurs at the gold/ceria interface. Here, we have investigated the dynamic changes of supported gold NPs with various sizes in a carbon monoxide oxidation atmosphere using deep potential molecular dynamics simulations. Our results reveal that the structure of tiny gold particles in carbon monoxide atmospheres becomes highly disordered and undergoes phase transition. Such a liquid-like structure provides massive reactive sites, enabling facile carbon monoxide oxidation on the solid-state gold NP rather than just at the gold/ceria interface. This result is further corroborated by catalytic experiments. This work sheds light on both the size effects and activity in noble metal catalysis and provides insights for the design of more effective nanocatalysts.