The content of copper in natural water is very low, and direct determination is difficult. Therefore, it is very meaningful for the combination of efficient separation-enrichment technology and highly sensitive detection. Based on the high adsorption capacity of Cu(Ⅱ) onto nano-sized ZnO, a novel method by using nano-sized ZnO as adsorbent and graphite furnace atomic absorption spectrometry as determination means was in this work. The adsorption behaviors of Cu(Ⅱ) on nano-sized ZnO was studied. Effects of acidity, adsorption equilibrium time, adsorbent dosage and coexisting ions on adsorption rates were investigated. The results showed that the adsorption efficiency was above 95% in a pH range from 3.0 to 7.0. Compared with other adsorbents for trace element enrichment such as activated carbon, nano-sized TiO2 powder, the most prominent advantage is nano-sized ZnO precipitate with the concentrated element can directly dissolved in HCl solution without any filtration and desorption process can directly analyzed by graphite furnace atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry. Compared with colloid nano materials, nano-sized ZnO is the true solution after dissolving have small matrix effect and viscosity more suitable for graphite furnace atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry detection. The proposed method possesses low detection limit (0.13 μg·L-1) and good precision (RSD=2.2%). The recoveries for the analysis of environmental samples were in a rang of 91.6%～92.6% and the analysis results of certified materials were compellent by using the proposed method.