In this work, layered double hydroxides (LDHs) including the variable valence Co2+ ions (CoAl-LDHs) is discovered to be capable of serving as the support and the reducing agent for the fabrication of well-distributed PdAu nanoparticles because of the low potential for reduction. Specifically, the active metal precursors undergo the redox process, in which Co2+ is oxidized to Co3+, while active metal ions are successfully reduced to bimetallic PdAu nanoparticles with the dispersion of 73%. Furthermore, the obtained catalysts are evaluated in the selective oxidation of benzyl alcohol as the probing reaction to explore the catalytic behavior. As for intrinsic activity, PdAu/CoAl-LDHs derived by the above in situ spontaneous reduction exhibits activation energy of 62.4 kJ mol−1, much lower than that of PdAu/CoAl-LDHs prepared by sol-immobilization. When the reaction time reaches to 4 h, the benzaldehyde selectivity over the former catalyst is up to 94%, originating from the surface electron starvation of active metals that promots the hydroxyl groups reacting with O2 to produce benzaldehyde.Graphic Abstract: