In this report, we introduced poly(n-vinylpyridine) (PnVP, n = 2, 4) as an electron-donating stabilizer for small (<2 nm) Au clusters and elucidated how coordinating pyridines affect the physical, optical, chemical, and catalytic properties of Au clusters. Spectroscopic measurements and theoretical calculation suggested the high electron-donating ability of PnVP. PnVP-stabilized Au dusters improved robustness in aerobic oxidation of alcohols compared to poly(N-vinyl-2-pyrrolidone)-stabilized ones, while retaining catalytic activities.