The electrochemical behaviors and sensing application of 100nm-gold plate electrode based on 6-amino-1-hexanethiol (6-AHT) self-assembled monolayer (SAM) have been investigated in this paper. The 6-AHT assembled nano gold plate electrode exhibited a nice linear potential performance of responding to Hg2+ in the range of 1.0×10-8—1.0×10-6 mol/L with a slope of 42.57 mV/-pC (25°C) in Tris-HCl buffer solution (pH=5.0). No obvious interferences were observed from Na+, K+, Ba2+, Mg2+, Ca2+, and Cr3+. The detection limit can be evaluated to 8.0×10-9 mol/L. In addition, the electrode possessed good stability and reproducibility with a recovery rate of 96.50-103.67%, indicating that it can be used for the determination of Hg2+ content in environmental waste water samples. The sensing mechanism of 6-AHT monolayer has also been discussed by the formation of coordination structure between amino groups of the thiol molecules and the mercury ions.