Al2O3 supports were prepared by a precipitation method using various basic solutions (NaOH, KOH, NH4OH, and Na2CO3) as precipitation agents, and Pt/Sn/Al2O3 nano-catalysts were then prepared by a sequential impregnation method. The prepared catalysts were applied to the direct dehydrogenation of n-butane to n-butenes and 1,3-butadiene. The effect of precipitation agents on the physicochemical properties and catalytic activities of Pt/Sn/Al2O3 nano-catalysts in the direct dehydrogenation of n-butane was investigated. Catalytic performance of Pt/Sn/Al2O3 nano-catalysts decreased in order of Pt/Sn/Al2O3 (NaOH) > Pt/Sn/Al2O3 (KOH) > Pt/Sn/Al2O3 (NH4OH) > Pt/Sn/Al2O3 (Na2CO3). Among the catalysts tested, Pt/Sn/Al2O3 (NaOH) nano-catalyst showed the best catalytic performance in terms of yield for total dehydrogenation products (TDP, n-butenes and 1,3-butadiene). Hydrogen chemisorption experiments revealed that platinum surface area of the catalyst was closely related to the catalytic performance. Yield for TDP increased with increasing platinum surface area of the catalyst.