Au single atoms and clusters were stabilized on Mg‐Al layered double hydroxide nanoparticles (LDH NPs), and the obtained Au@LDH NPs were supported on SiO2 and CeO2. After hydrogen reduction, Au single atoms were found together with Au clusters on LDH/SiO2. In contrast to Au single‐atom catalysts which are deposited in metal vacancies of oxide supports, the LDH NPs stabilize small Au species despite the absence of metal vacancies. The obtained Au(0)@LDH/SiO2 catalyzed aerobic oxidation of alcohols, and Au single atoms maintained after the reaction. Given that only Au NPs were observed on bulk LDH, the abundant surface OH group of LDH NPs would contribute to stabilize Au, resulting in higher activity than Au/LDH‐bulk. After calcination to transform LDH to mixed metal oxide (MMO), the obtained Au(0)@MMO/SiO2 also exhibited high catalytic activity. Moreover, Au(0)@LDH/CeO2 exhibited higher activity and excellent selectivity for hydrogenation of 4‐nitrostyrene to 4‐aminostyrene than conventional Au catalysts such as Au/CeO2 and Au/TiO2 even though only Au NPs were present. We demonstrated that Au size can be minimized using LDH NPs, exhibiting in high catalytic performance. The basic surface OH groups of LDH would be also beneficial for deprotonation of alcohols and heterolytic H2 dissociation in the catalytic reactions.