This work describes a new one-step method for the preparation of AuNP/LDH nanocomposites via the polyol route. The novelty of this facile, simple synthesis is the absence of additional reactants such as reductive agents or stabilizer, which gives the possibility to obtain phase-pure systems free of undesiderable effect. The AuNP formation is confirmed by SEM, TEM, PXRD, and XAS; moreover, the electrochemical characterization is also reported. The electrocatalytic behavior of AuNP/LDH nanocomposites has been investigated with respect to the oxidation of methanol in basic media and compared with that of pristine NiAl-Ac. The 4-fold highest catalytic efficiency observed with AuNP/LDH nanocomposites suggests the presence of a synergic effect between Ni and AuNP sites. The combination of these experimental findings with the low-cost synthesis procedure paves the way for the exploitation of the presented nanocomposites materials as catalysts for methanol fuel cells.