Contributions of electronic (or ligand) and geometric (or ensemble) effects on the AuM bimetallic nano-catalyst were elucidated by using a simple aerobic oxidation of 1-phenylethanol to acetophenone on the basis of difference in the ionization energy values (Ei) between Au and M elements. The poly(N-vinylpyrrolidone) (PVP)-protected Au60M40 bimetallic NPs (M = Ag, Cu, Pd, Pt and Ir) were prepared with a polyol reduction method, and stabilized onto the solid base hydrotalcite support affording the Au60M40-PVP/HT catalysts. The yields for acetophenone were observed as the following order; Au60Pd40-PVP/HT (>99%) >> Au60Ag40-PVP/HT (17.4%) > Au60Cu40-PVP/HT (13.8%) > Au60Pt40-PVP/HT (7.1%) > Au60Ir40-PVP/HT (5.5%), at 343 K for 6 h. Differences in the Ei between Au and M (EiAu-EiM) indicted that the yields over the Ag, Cu, Pt, and Ir incorporated Au catalysts were well-understood on the ligand effects theory, though geometric factors such as differences in nanostructure around Au atom in Au60M40 NPs on HT should be further considered as other contributed factors. The significant activity on Au60Pd40-PVP/HT was studied in terms of the electron density of Pd atoms. It was observed that the Pd 4d density was varied by the amount of Au loading. According to these observations combined with our previous studies, we suggest that the advantages in AuPd bimetallic catalyst are not only in the ligand effect serving negatively-charged Au but also the ensemble effect of neighbor Pd, and they synergistically contribute to the novel activity for aerobic alcohol oxidation over AuPd catalyst.