Synthesis of N, N, N’, N’-tetramethyl-1,6-hexanediamine(TMHDA) by the amination of 1,6-hexanediol(HDO) and dimethylamine(DMA) at normal pressure over an outstanding Cu/Ni/Zn catalyst supported on aluminum oxide(γ-Al2O3) was studied in this article. Cu/Ni/Zn/γ-Al2O3(Cu: Ni: Zn = 28: 7: 12) exhibited excellent catalytic performance, which HDO was almost completely transformed and TMHDA reached 85 % selectivity at 200 °C. The amination of HDO required two hydrogenations and two dehydrogenations, and the selectivity of the amination catalyst depended on the balance of dehydrogenation and hydrogenation. Various characterization (TEM, BET, XRD, H2-TPR, XPS) demonstrated that the addition of Zn to the Cu/Ni catalyst could reduce the agglomeration of Cu/Ni particles and change the valence distribution of Cu. The Cu/Ni/Zn/γ-Al2O3 catalyst was a very promising and green method for the synthesis of tertiary diamines through amination of diols.