Benzyl alcohol was chosen as a model substrate for Pd/hydrotalcite mediated selective oxidation of alcohols to investigate the roles of palladium precursors (Na2PdCl4, K2PdCl4, PdCl2), reduction reagents (N2H4 and NaBH4), and Pd loading amount in determining structure-activity relationship of flower-like nano-catalyst. XRD analyses show typical characteristic peaks of all hydrotalcites regardless of palladium precursors; whereas TEM studies show a larger mean size of Pd nanoparticles obtained with reducing reagent N2H4 over NaBH4. However, the difference in particle sizes didn't result in a significant difference in benzyl alcohol conversion, but extended to catalytic selectivity where N2H4-reduced Pd/hydrotalcite achieved 94%-96% selectivity over 88%-93% by NaBH4. FTIR-CD3CN surface acidity study suggested that a stronger acidity of N2H4 reduced Pd/hydrotalcite may account for its better selectivity. 3% Pd/hydrotalcite with N2H4 as reducing reagent demonstrated the best catalytic performance; and was successfully extended to oxidation of 17 aromatic and aliphatic alcohols. The conversion of alcohols is strongly dependent on individual alcohol molecular structure and electronic effect; but all reactions showed medium-to-excellent selectivity.